WBS 231200 - Biomass conversion to Acrylonitrile monomer-precursor for the production of carbon fibers

March 8 2017Biochemical conversion

This presentation does not contain any proprietary confidential or otherwise restricted information

US Department of Energy (DOE)Bioenergy Technologies Office (BETO)

2017 Project Peer Review

PI Amit GoyalSouthern Research

Goal Statement Goal Develop a novel commercially viable cost effective thermochemical

process that enables utilization of an alternative feedstock - non-food sugars for the production of acrylonitrile (ACN) ndash an essential precursor for high performance carbon fiber

Laboratory (phase I ongoing) and bench (phase II future) scale demonstration

2

Supports DOE BETOrsquos strategic goals aimed for conversion RampD and BETOrsquos modeled $1lb cost goals for Bio-ACN production to reduce carbon fiber manufacturing cost to $5lb by 2020

ACN production from different routes1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

Carbon fiber

Quad Chart Overview Timelinebull Project start date Feb 1st 2015bull Project end date March 30th 2017bull Percent complete 95 Partnersbull Southern Research (70) Cytec-Solvay (25)

NJIT (5)bull Arbiom Renmatix and NCSU ndash Sugar suppliers

3

bull Ct-A Feedstock Variabilitybull Ct-H Efficient Catalytic

Upgrading of sugarsaromatics Gaseous and Bio-Oil Intermediates to Fuels and Chemicals

bull Ct-I Product Finishing Acceptability and Performance

Budget

Barriers

Total Costs FY 12-14

FY 15 Costs

FY 16 Costs

Total Planned Funding (FY17 ndash Project End Date)

DOE Funded $333333 $862130 $593108 Project total cost share $94593 $173806 $233731

Southern Research $93238 $149849 $186523 Cytec-Solvay $0 $23512 $34806 NJIT $1355 $445 $12402

Context Carbon fiber ndash strength of steel weight of plastic

Widespread use of carbon fiber restricted due to high cost of production

Production of carbon fiber precursor chemicals eg ACN is a potentially viable area to reduce the cost of making carbon fibers

1 - Project Overview

4

DOE estimates carbon fiber production cost needs to be at $5lb equivalent to $1lb cost of the precursor

ACN production from non-petroleum feedstock is limited to purified glycerol available at high cost1

Petroleum based processes are affected by volatile propylene price and shortage most recently due to preference for low cost ethane

1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

1 - Project Overview (contd)

5

C5 C6sugars

H2

R1

Co-Product

S-1

Glycerol+PG

R2

Co-Product

S-2

Acrolein

R3

S-3

Bio-ACN

Vendor Cytec-Solvay Southern Research

Project goalsobjective Multistep catalytic (R1-R3) ACN production at lt$1lb Development of 2 novel (R1 amp R2) and 1 known (R3) catalysts to meet target Process intensification via novel one step sugar to Glycerol and PG conversion Use of known technologies to separate undesirables main and co-products

NH3

Air

R1 = Hydrocracking R2 = Dehydration R3=AmmoxidationS-1 to S-3 = Separation trains PG = Propylene glycol

Schematic of the proposed sugar to ACN process

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Goal Statement Goal Develop a novel commercially viable cost effective thermochemical

process that enables utilization of an alternative feedstock - non-food sugars for the production of acrylonitrile (ACN) ndash an essential precursor for high performance carbon fiber

Laboratory (phase I ongoing) and bench (phase II future) scale demonstration

2

Supports DOE BETOrsquos strategic goals aimed for conversion RampD and BETOrsquos modeled $1lb cost goals for Bio-ACN production to reduce carbon fiber manufacturing cost to $5lb by 2020

ACN production from different routes1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

Carbon fiber

Quad Chart Overview Timelinebull Project start date Feb 1st 2015bull Project end date March 30th 2017bull Percent complete 95 Partnersbull Southern Research (70) Cytec-Solvay (25)

NJIT (5)bull Arbiom Renmatix and NCSU ndash Sugar suppliers

3

bull Ct-A Feedstock Variabilitybull Ct-H Efficient Catalytic

Upgrading of sugarsaromatics Gaseous and Bio-Oil Intermediates to Fuels and Chemicals

bull Ct-I Product Finishing Acceptability and Performance

Budget

Barriers

Total Costs FY 12-14

FY 15 Costs

FY 16 Costs

Total Planned Funding (FY17 ndash Project End Date)

DOE Funded $333333 $862130 $593108 Project total cost share $94593 $173806 $233731

Southern Research $93238 $149849 $186523 Cytec-Solvay $0 $23512 $34806 NJIT $1355 $445 $12402

Context Carbon fiber ndash strength of steel weight of plastic

Widespread use of carbon fiber restricted due to high cost of production

Production of carbon fiber precursor chemicals eg ACN is a potentially viable area to reduce the cost of making carbon fibers

1 - Project Overview

4

DOE estimates carbon fiber production cost needs to be at $5lb equivalent to $1lb cost of the precursor

ACN production from non-petroleum feedstock is limited to purified glycerol available at high cost1

Petroleum based processes are affected by volatile propylene price and shortage most recently due to preference for low cost ethane

1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

1 - Project Overview (contd)

5

C5 C6sugars

H2

R1

Co-Product

S-1

Glycerol+PG

R2

Co-Product

S-2

Acrolein

R3

S-3

Bio-ACN

Vendor Cytec-Solvay Southern Research

Project goalsobjective Multistep catalytic (R1-R3) ACN production at lt$1lb Development of 2 novel (R1 amp R2) and 1 known (R3) catalysts to meet target Process intensification via novel one step sugar to Glycerol and PG conversion Use of known technologies to separate undesirables main and co-products

NH3

Air

R1 = Hydrocracking R2 = Dehydration R3=AmmoxidationS-1 to S-3 = Separation trains PG = Propylene glycol

Schematic of the proposed sugar to ACN process

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Quad Chart Overview Timelinebull Project start date Feb 1st 2015bull Project end date March 30th 2017bull Percent complete 95 Partnersbull Southern Research (70) Cytec-Solvay (25)

NJIT (5)bull Arbiom Renmatix and NCSU ndash Sugar suppliers

3

bull Ct-A Feedstock Variabilitybull Ct-H Efficient Catalytic

Upgrading of sugarsaromatics Gaseous and Bio-Oil Intermediates to Fuels and Chemicals

bull Ct-I Product Finishing Acceptability and Performance

Budget

Barriers

Total Costs FY 12-14

FY 15 Costs

FY 16 Costs

Total Planned Funding (FY17 ndash Project End Date)

DOE Funded $333333 $862130 $593108 Project total cost share $94593 $173806 $233731

Southern Research $93238 $149849 $186523 Cytec-Solvay $0 $23512 $34806 NJIT $1355 $445 $12402

Context Carbon fiber ndash strength of steel weight of plastic

Widespread use of carbon fiber restricted due to high cost of production

Production of carbon fiber precursor chemicals eg ACN is a potentially viable area to reduce the cost of making carbon fibers

1 - Project Overview

4

DOE estimates carbon fiber production cost needs to be at $5lb equivalent to $1lb cost of the precursor

ACN production from non-petroleum feedstock is limited to purified glycerol available at high cost1

Petroleum based processes are affected by volatile propylene price and shortage most recently due to preference for low cost ethane

1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

1 - Project Overview (contd)

5

C5 C6sugars

H2

R1

Co-Product

S-1

Glycerol+PG

R2

Co-Product

S-2

Acrolein

R3

S-3

Bio-ACN

Vendor Cytec-Solvay Southern Research

Project goalsobjective Multistep catalytic (R1-R3) ACN production at lt$1lb Development of 2 novel (R1 amp R2) and 1 known (R3) catalysts to meet target Process intensification via novel one step sugar to Glycerol and PG conversion Use of known technologies to separate undesirables main and co-products

NH3

Air

R1 = Hydrocracking R2 = Dehydration R3=AmmoxidationS-1 to S-3 = Separation trains PG = Propylene glycol

Schematic of the proposed sugar to ACN process

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Context Carbon fiber ndash strength of steel weight of plastic

Widespread use of carbon fiber restricted due to high cost of production

Production of carbon fiber precursor chemicals eg ACN is a potentially viable area to reduce the cost of making carbon fibers

1 - Project Overview

4

DOE estimates carbon fiber production cost needs to be at $5lb equivalent to $1lb cost of the precursor

ACN production from non-petroleum feedstock is limited to purified glycerol available at high cost1

Petroleum based processes are affected by volatile propylene price and shortage most recently due to preference for low cost ethane

1Guerrero-Peacuterez et al Catalysis Today 239 (2015) 25-30

1 - Project Overview (contd)

5

C5 C6sugars

H2

R1

Co-Product

S-1

Glycerol+PG

R2

Co-Product

S-2

Acrolein

R3

S-3

Bio-ACN

Vendor Cytec-Solvay Southern Research

Project goalsobjective Multistep catalytic (R1-R3) ACN production at lt$1lb Development of 2 novel (R1 amp R2) and 1 known (R3) catalysts to meet target Process intensification via novel one step sugar to Glycerol and PG conversion Use of known technologies to separate undesirables main and co-products

NH3

Air

R1 = Hydrocracking R2 = Dehydration R3=AmmoxidationS-1 to S-3 = Separation trains PG = Propylene glycol

Schematic of the proposed sugar to ACN process

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

1 - Project Overview (contd)

5

C5 C6sugars

H2

R1

Co-Product

S-1

Glycerol+PG

R2

Co-Product

S-2

Acrolein

R3

S-3

Bio-ACN

Vendor Cytec-Solvay Southern Research

Project goalsobjective Multistep catalytic (R1-R3) ACN production at lt$1lb Development of 2 novel (R1 amp R2) and 1 known (R3) catalysts to meet target Process intensification via novel one step sugar to Glycerol and PG conversion Use of known technologies to separate undesirables main and co-products

NH3

Air

R1 = Hydrocracking R2 = Dehydration R3=AmmoxidationS-1 to S-3 = Separation trains PG = Propylene glycol

Schematic of the proposed sugar to ACN process

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Activity(Phase I-Ends March 302017)

Taskowner Milestone

Task 1 Micro Reactor set up SR Setup completed

Task 2 Catalyst development and testing

Task 21 Develop R1 catalystTask 22 Parametric study for R1Task 23 Develop R2 catalyst Task 24 Parametric study for R2Task 25 Optimize ACN productionTask 26 Measure catalyst stability and regeneration

SR At least 2 novel candidates for each of R1 and R2 R3 lit catalystR1 S(glycerol+PG) gt65 gt50glhrR2 S(acrolein) gt 70 gt375glhr R3 S(ACN) gt 70 gt75 glhrCatalyst life gt40h for each catalyst

Task 3 Catalyst characterization NJITSR Completed (fresh and used catalyst)

Task 4 Bio-ACN validation Cytec-Solvay

Model impure ACN validated 3 product samples tested

Task 5 TEALCA SR Preliminary TEA completed with lab scale data Cost lt$1lb

Task 6 Project Management andReporting

SR Deliverables to DOE-EERE

6

2 ndash Approach (Management)

Data transfer Material transfer

(Months)

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

7

Activity(Phase II- Future)

Taskowner Milestone

Task 7 Bench scale unit

Task 71 Optimal safety and storageconditionsTask 72 Separation methods designTask 73 Commissioning

SR Complete design specs and transfer to EPC Commission units and complete preliminary readiness test

Task 8 Continuous operation SR 500hrs of operation 500kgs of ACN

Task 9 Periodic ACN validation NJITSR ACN validation every 40hr

Task 10 Characterization Cytec-Solvay

To determine regeneration if required

Task 11 TEALCA SR lt$1lb cost lt35 GHG emission

Task 12 Project Management andReporting

SR Deliverables to DOE-EERE

(Months)

Dr Amit Goyal (PI)Dr Santosh Gangwal (Co-PI)Dr Jadid Samad (Engineer)

Lindsey Chatterton (Chemist)Zora Govedarica (Chemist)

Dr Zafar IqbalDr El Mostafa Benchafia

Dr Longgui TangMr Billy Harmon

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Model C5C6 sugar- Sugar with impurities

- Catalyst screening- Performance metrics

- Parametric study- T P impurity

- TEA

2 ndash Approach (Technical)

8

- Catalyst designsynthesis- Characterization (NJIT)- Reaction evaluation

- Glycerol PG- Catalyst screening

- Performance metrics- Parametric study

- O2- TEA

- Literature catalyst- Characterization (NJIT)- Reaction evaluation

- Acrolein (AC)- Catalyst screening

- Performance metrics- Parametric study

- O2 NH3 AC conc - 50g ACN- TEA

- 500 kg ACN- Continuous operation- Final TEALCA

R2 Dehydration (Task 23)R3 Ammoxidation (Task 23)

Phase II Bench scale(Future)

R1 Hydrocracking (Task 23)

Reactor setup(Task 1)- gm scale - Meaningful scale-up- Analytical procedure

ACN validation(Task 4)- ACN baseline with impurity (Cytec)- Product ACN (Cytec)

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

2 ndash Approach (Technical)

9

Critical success factors (GoNo Go decision points) Cost of production lt$1lb 1kg of recoverable product per 334 kg non-food sugar (~30 mass recovery) Validity of purified Bio-ACN as a carbon fiber ready monomer

Challenges Final product specification at different sugar impurity levels Catalyst deactivation Extent of separation required prior to each reaction step

Reaction Productivity (glhr)

Desired product

Yield () Catalyst life (hr)

R1 gt50 Glycerol + PG gt65 gt40R2 gt375 Acrolein gt70 gt40R3 gt75 ACN gt70 gt40

Progresstarget metrics

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

3- Technical accomplishmentsprogressresults Task 2 Catalyst development amp testing Catalyst development At least two novel catalysts for each of R1 and R2

developed that fully meet performance target for sugar to polyols and Glycerol to acrolein

Catalyst testingndash Single step with mild operating conditions (TP) used (R1)ndash Model and commercial (with impurities) sugar feeds from two different

vendors tested (R1)ndash Product specification tested with varying degrees of feed impurities (R1)ndash Glycerol and PG to acrolein conversion tested on same catalysts (R2)ndash Alternative pathway proposed using PG as co-product (R2)ndash Catalyst lifetime verified and regeneration method established with long term

testing (R1-R3) Task 4 ACN validation

- Optimized performance and product validation completed Task 5 TEA LCA

- Preliminary cost analysis and separation simulation conducted- Cost distribution and sensitivity analysis with respect to raw material price

reveals extent of risk 10

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

11

3 ndash Technical Accomplishments ProgressResults

H2 -xH2O

P = 600-750 PSIG 170-240degC

(novel transition mixed metal catalyst)

sugar Glycerol PropyleneGlycol (PG)

EthyleneGlycol (EG)

R1Hydrocracking

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

12

Products Glycerol+PG (~11) and EG(lt5)

High selectivity at different feed types and C5C6 ratios

Sugar type Conv ()

Yield ()

Model feedGlucose (G) 100 81Xylose (X) 100 95G 25-X 75 100 96G 50-X 50 100 83G 75-X 25 100 81

Impure feedHydrolyzate 100 76Bagasse 100 76Pure Hydrolyzate 100 79

Catalyst stable at high temperature in aqueous phase

Littleno phase change

Catalyst life gt 100hr

Low H2 requirement (~004-005kg H2kg sugar) Productivity ndash 50 glhr

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

13

Effect of sugar impurities Catalytic runs using sugars from commercial vendors Different levels of metallic as well as organic impurities High levels of impurity negatively affected catalyst activity and more

importantly final product specification (Purification necessary)

Characteristics

Hydrolysis method Method 1 Method 1 Method 2 Method 2

Sugar type Oligomer Oligomer Monomer Monomer

Metalion impurities[mgkg] 4532 84 2270 129

Organic impurities [gkg] 23 28 10 82

pH 33 29 higher 33

Hydrocracking Results Hydrolyzate conversion to polyols

Hydrolyzate Conv[] 47 75 100 100

Overall selectivity [] 79 85 70 81

Performance stability 44 hrs gt 48 hrs gt 32 hrs gt120 hrs

Meets product specs No Yes No Yes

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

14

3 ndash Technical Accomplishments ProgressResultsR2Dehydration

Glycerol (BP 290degC)

Propylene glycol (PG)(BP 1882degC)

Acrolein(BP 526degC)

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

15

0

01

02

03

0

25

50

75

100

Acid-base Acid only Tota

l aci

dity

[mm

ole

g]

S [ac

role

in

]

Bronsted Lewis Sacrolein ()

Target

0

25

50

75

100

Acid-base Acid only

S [ac

role

in

]

Target

Feed Glycerol Feed Propylene Glycol (PG)

Conversion = 100 Catalyst life up to 51 hrs Selectivity improves with BL ratio Productivity gt 350 glhr Performance meets target Acetol (hydroxyacetone) main by-

product

Conversion = 100 decreases with time (short catalyst life)

Performance does not meet target Propanal main by-product

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Moving forward with PG Alternative Approachbull Poor acrolein yield from PG (42 max)bull Higher selectivity (gt50) to propionaldehyde ndash complex separation from

acrolein due to similar boiling points (49degC vs 526degC for acrolein)bull An alternative approach could be to separate PG from Glycerol prior to

dehydration reaction and use it (PG) as a high value co-product

16

H2

R1

Co-Product

S-1

Glycerol+PG

Originally proposed

H2

R1

PG

S-1

Glycerol

Alternative approach

C5 C6sugars

C5 C6sugars

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

17

3 ndash Technical Accomplishments ProgressResultsR3Ammoxidation

Acrolein

400-450degC NH3 05 O2

Bi-MoSilica Acrylonitrile

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

18

BiMosilica catalyst Acrolein (AC) evaporated from 90 pure feed High selectivity (gt90) to Acrylonitrile (ACN) Other by-products are acetonitrile (AN) and propionitrile (PN)

Catalyst optimization(Parametric study)

Long term run at optimized conditions NH3AC = 10 O2AC=10 for GHSV=9675h-1 and GHSV = 7661h-1

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

ACN validation

19

Bio-mass ACN sample Sample-1 Sample-2 Sample-3

Appearance Clear Slightly pink ClearProduct composition (wt)

Basis Wet Dry Wet Dry Wet DryActual ACN wt 169 159 431 8528 511 983

Waterwt ~89 - ~95 - ~95Impurities

Acetone wt 001 001 0 0 0Acrolein wt 784 7375 0 0 0

Acetonitrile wt 013 125 074 147 010 002Propionitrile wt 096 902 0 0 0

Very low impurity level Excess water due to use of acetic acid solution to neutralize excess NH3

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

20

3 ndash Technical Accomplishments ProgressResults

TEALCA

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

21

Category Proposed AlternativeSeparation of GlycerolPG No YesACN yield wt 27 20Recoverable product yield wt ~34 ~40Co-product Acetol PG AcetolCo-product lblb ACN 025 (Acetol) 16 (PG) 025 (Acetol)Overall carbon efficiency 60 80

ACN production cost ($lb ACN) 078 073

Preliminary TEAComparison between originally proposed and alternative process

Higher ACN yield from proposed route as both Glycerol and PG used for ACN production

Separating PG (alternative process) improves carbon efficiency ACN production cost calculated based on 5000 MTyear production

capacity More efficient co-product recovery makes the alternative process more

economic

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Distribution of cost in ACN production

Catalyst price contributes small fraction of the cost due to use of non-precious metal catalysts

Maximum cost contribution from raw materials in particularly sugar Overall low H2 and NH3 requirement as raw materials Sensitivity analysis of ACN production cost with respect to raw materials price

essential

Cost distribution pie charts

22

Proposed

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Chart1

Original

00168

0056

0204

0525

0124

0075

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Case b

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sheet1

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

ideal

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

ideal

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

Alternative

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

Chart1

Alternative

00148771218

01159396612

01907419626

05221033678

00823431597

00739947269

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

Catalyst
Utility
Capital cost
Sugar
Hydrogen
Ammonia

case a

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Production Rate			5000		MTA
					Case a
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		25000		MTyear		3157		kghr		Sugar		lb		$ 016		500000		$ 079		$ 05221					Water in =			9
Total product yield		04					Ammonia		lb		$ 021		060000		$ 013		$ 00823					H2 in =			005
ACN yield		02					Hydrogen		lb		$ 045		025000		$ 011		$ 00740					Glycerol out			049
Propanal yield		02					Catalyst										PG out			040
Propanal production		5000		Mtyr				Reactor 1		lb		$ 1814		000095		$ 002		$ 00113					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000041		$ 000		$ 00031					Water			909
Catalyst mass		15783		kg				Reactor 3		lb		$ 1134		000007		$ 000		$ 00005		$ 00149
Time on stream		90						Total utilities
					Methane		mm BTU		$ 300		005876		$ 018		$ 01159
Reactor 2						Capital cost		lb				$ 029		$ 01907
Catalyst mass		9154		kg				By product credit		lb		$ (064)		105		$ (067)					Reactor 2		Glycerol in=			047
Time on stream		67						Total cost		lb				$ 073						PG in =			011
							-037		0344		-012728						Water in =			909
Reactor 3															EG in =			002
Catalyst mass		1169		kg							Case a							Acrolein out =			025
Time on stream		90								Raw materials		678			Sugar		770
							Catalyst		15			Hydrogen		121
Utitlities								Utility		116			NH3		109
002590731		mmBTUhrkg Biomass							Capital cost		191
								1000
													Reactor 3		Acrolein in =			024
						$lb		Hydrogen price($ton)		Cost of ACN ($lb)							Air in			227
						03404448479		750		07							O2 in =			053
						04539264639		1000		073							NH3 in =			012
						05674080799		1250		076							Water in =			023
						06808896959		1500		079
						07943713118		1750		081							ACN out =			020
						09078529278		2000		084
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						00907852928		200		$ 039
						0113481616		250		$ 050
						01361779392		300		$ 061
						01588742624		350		$ 073
						01815705856		400		$ 084
						02042669088		450		$ 095
						0226963232		500		$ 107
						$lb		Sugar price($ton)		Cost of ACN ($lb)
						01861098502		410		$ 071
						02088061734		460		$ 073
						02315024966		510		$ 074
						02541988198		560		$ 075
						0276895143		610		$ 077
						02995914662		660		$ 078
						03222877894		710		$ 079

case a

Cost of ACN ($lb)

Cost of H2 $ton

Cost of ACN $lb

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sensiplot

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sheet2

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Case b

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

Separation post reactor I to enable low EG concentration and high Glycerol recovery
RowCase		Status
		VARY 1		R2GLY		R2PG		R2EG		R2EGX		REBD
		D1
		COL-SPEC
		DF
			KGHR		KGHR		KGHR			KJHR
1		OK		06		135819593		201829952		646725956		00398057425		12378009
2		OK		0605263158		135803455		186465903		622539378		00387450042		125597106
3		OK		0610526316		135786987		171286418		596867104		00375660206		127444747
4		OK		0615789474		135770302		156309439		569555563		00362549599		129324149
5		OK		0621052632		135753389		141561004		54039327		00347936301		131239905
6		OK		0626315789		135736235		127070152		509144641		00331614537		133197487
7		OK		0631578947		135718818		112868893		475550138		00313353508		135203484
8		OK		0636842105		135701113		989920142		439327982		293E-02		137265914
9		OK		0642105263		135683088		854766133		400177844		270E-02		139394636
10		OK		0647368421		135664681		72361111		357790643		244E-02		141601997
11		OK		0652631579		135645818		596839192		311858345		215E-02		14390357
12		OK		0657894737		135626537		474789447		262101943		183E-02		146317937
13		OK		0663157895		135606163		357803739		208288311		147E-02		148872479
14		OK		0668421053		135583994		246058686		150321063		108E-02		151601114
15		OK		0673684211		135556343		139587372		884224587		642E-03		15455263
16		OK		0678947368		135475006		395915596		24863348		183E-03		157845385		Glycerol recovery			984
17		OK		0684210526		134011194		037908944		0211356012		158E-04		161963095
18		OK		0689473684		131816681		0184566569		00986158093		748E-05		165097067
19		OK		0694736842		129594358		0123457037		00643876061		497E-05		167713592
20		OK		07		127365852		0092324343		00473484947		372E-05		170096096
21		OK		061		135788758		172794851		599503848		00376895156		127259428

Sheet1

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

ideal

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		370370		0539			0524510407				Water in =			9
Total product yield						Ammonia		lb		$ 021		066667		0128			01240841763				H2 in =			005
ACN yield		027					Hydrogen		lb		$ 045		018519		0077		$ 07441		00749300581		07235246414			Glycerol out			049
Acetol yield		014					Catalyst							0				PG out			040
					Reactor 1		lb		$ 1814		000070		0012			0				EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000046		0005			0				Water			909
Catalyst mass		11691		kg				Reactor 3		lb		$ 1134		000008		0001		$ 00173		00167798801
Time on stream		90						Total utilities							0
					Methane		mm BTU		$ 300		002074		0057		$ 00571		00555097306
Reactor 2						Capital cost					0210		$ 02100		02041857479
Catalyst mass		10255		kg				By product credit		lb		$ (100)		025		$ (025000)					Reactor 2		Glycerol in=			049
Time on stream		67						Total cost					$ 077848						PG in =			039
					Propanal			$ (064)		031			$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1299		kg							078		$ 000152						Acrolein out =			036
Time on stream		90															HA out			014
						Raw materials		724			Sugar		725					Propanal			009
Utitlities							Catalyst		17			Hydrogen		171
001234701		mmBTUhrkg Biomass						Utility		56			NH3		104
						Capital cost		204
							1000							Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
					600		kghr		CAN								NH3 in =			018
					3157		kghr		sugar								Water in =			154
														ACN out =			030
					Acrolein
					25955283199
					132405424697			22003536765
					05101289926			00847747898		05949037823

ideal

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

	Case b														Case a
	Catalyst		168													Catalyst		149
	Utility		560													Utility		1159
	Capital cost		2040													Capital cost		1907
	Sugar		5250													Sugar		5221
	Hydrogen		1240		07235246414												Hydrogen		823
	Ammonia		750		0												Ammonia		740
			0
			0
			00167798801
			0
			00555097306					0524510407
			02041857479					01240841763
							00749300581

Original

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

Alternative

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Case b
Production Rate			5000		MTA
					Case b
Plant Capacity for ACN =		5000		MTyr				Type		Unit		Cost$unit		Consumption unitlb		Cost $lb					Streams
Production rate		631		kghr				Raw materials									Reactor 1		Xylose in=			1
Sugar needed		18519		MTyear		2338		kghr		Sugar		lb		$ 016		336134		0534		$ 11764706					Water in =			9
Total product yield						Ammonia		lb		$ 021		060504		0126		$ 2783193					H2 in =			005
ACN yield		02975					Hydrogen		lb		$ 045		016807		0076		$ 1680672		0736				Glycerol out			049
Acetol yield		014					Catalyst						$ - 0					PG out			040
Acetaldehyde yield		022					Reactor 1		lb		$ 1814		000064		0012		$ 254640					EG out			005
Reactor 1						Reactor 2		lb		$ 1134		000040		0004		$ 98766					Water			909
Catalyst mass		10610		kg				Reactor 3		lb		$ 1134		000007		0001		$ 17701		0017
Time on stream		90						Total utilities						$ - 0
					Methane		mm BTU		$ 300		003945		0118		$ 2609144
Reactor 2						Capital cost					0200		$ 4409200
Catalyst mass		65784		kg									$ - 0				Reactor 2		Glycerol in=			049
Time on stream		90						Acetaldehyde		ln		$ (046)		07394957983		$ (034017)						PG in =			039
					Total cost					$ 073114		$ - 0					Water in =			528
Reactor 3															EG in =			005
Catalyst mass		1179		kg													Acrolein out =			036
Time on stream		90									078		$ 004886						HA out			014
														Propanal			009
Utitlities
003945		mmBTUhrlb CAN
													Reactor 3		Acrolein in =			035
														Air in
														O2 in =			064
														NH3 in =			018
														Water in =			154
														ACN out =			030

ACN production cost shows high sensitivity to sugar price

lt$1lb within $300-$450ton sugar price

ACN production cost nearly insensitive to H2 and NH3 price change

Proposed Alternative

Sensitivity analysis

$460ton $1000ton

$350ton

23

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Preliminary LCA

24

Petroleumbased ACN

kg GHG kg ACN

Crude to Propylene

016

Propylene to ACN

286

Total 302

Biomass to ACN kg GHG kg ACN

Sugars to polyols (R1S1) 091

Polyols to Acrolein (R2S2) 042

Acrolein to ACN (R3S3) 056

Total 192

~37 reduction in greenhouse gas emissions compared to conventional petroleum based processes

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

25

Technical progress summaryTasks Milestone Achievements Meet

target21-22(R1)

ge 2 novel candidatesSelec(di-triols) gt65 Productivity gt50glhr

3 novel candidatesSelec(di-triols) gt75 Productivity gt50glhr

23-24(R2)

ge 2 novel candidatesSelec(acrolein)gt 70 Productivity gt375glhr

2 novel candidatesSelec(acrolein) 72-80 (Glycerol feed) and lt50 (PG feed) Productivity gt375glhr

Glycerol

PG

25 (R3) Selec (ACN) gt 70 Productivity gt75 glhr

Selec (ACN) 90-98Productivitygt75 glhr

26 Catalyst life gt 40h gt120h (R1) ~51h (R2) gt40h (R3) 4 ACN validation Product ACN validated Ongoing5 lt$1lb $073-078lb Ongoing6 Project reporting Reports delivered regularly to DOE Ongoing

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Supports BETOrsquos strategic goal of thermochemical conversion RampD ldquoDevelop commercially viable technologies for converting biomass into energy dense fungible finished liquid fuels such as renewable gasoline jet and diesel as well as biochemicals and biopowerrdquo

Contributes to overcoming the technical challenges and barriers in this area byndash Design and discovery of new low-cost catalysts for biomass conversion ndash Process intensification via single step sugar conversion

Relevance to industry and market placendash Alternative low cost feedstock Price and supply of propylene volatile Biomass is

abundant and the price of derived sugar is more stable ndash H2 requirement and C efficiency Less H2 use but high C efficiency (80)ndash Heat management Lower heat capacity of acrolein than glycerol Requires less

energy to heat acrolein than glycerol (advantage over direct ammoxidation of glycerol)ndash Process integration Integrable to commercial ACN production processesndash Low cost production Production of ACN at lt$1lb paves way for reducing cost of

carbon fiber productionndash Co-production of PGacetol Alternative low cost pathway for the production of high

value chemicals and their use as co-productsndash Plant scale Relatively small scale (5000 MTYear) ACN plants needed to feed Carbon

fiber lines (2 lines or 1000 MTyear)

4 ndash Relevance

26

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

4 ndash Relevance

27

AcrylonitrileManufacturers

Catalyst Manufacturers

Investor Groups Sugar Suppliers

Three companies interested ndash USA Japan and India

and partner Cytec-Solvay

Working with a major catalystmanufacturer to scale-up and toll-produce kilogram quantities of catalyst for Phase II

Working with a group of investor with experience in development of early stage chemicals technology ndash for joint development and toaccelerate phase II research with further interest in funding first commercial plant

Working with two commercial vendors ndashArbiom and Renmatix ndash for sugar supplies for Phase I and Phase II

Technology Transfer - Initiatives

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

5 ndash Future Work For ongoing Phase I (ending on March 2017)

ndash Produce 50 grams of ACNndash ACN product validation ndash Update TEALCAndash Phase I final report and deliverables

28

Stage Gate Review ndash Phase I ndash After March 30th 2017

Phase II ndash Validating prototype system- Continuous bench scale unit design for kgshr production- Integrated and slip stream separations to achieve productby-product purities- Continuous 1000 hr operation for the production of up to 500kg ACN- Product stabilization and safe operations for hazardous products- Finalize TEALCA- Continue discussion with potential partners - Complete final project report

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

29

Summary Overview Novel thermocatalytic and economically viable process for the

conversion of biomass derived non-food sugars to acrylonitrile

Approach Novel inexpensive stable catalyst development mild operating conditions separation of co-products and undesirables scalability TEALCA and sensitivity analysis

Technical progress Process flexible to sugar types High performance catalysts meet target for sugar to oxygenates glycerol to acrolein and acrolein to ACN conversion Requires less H2 and NH3 as raw materials Production of high value PG and acetol as co-products Economics favorable (lt$1lb) at wide range of sugar price

Challenges PG conversion to acrolein meeting product specifications at different sugar impurity levels

Relevance Supports BETOrsquos conversion RampD strategic goal

Future work Scale up to bench scale Detail TEALCA Product validation

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Acknowledgements

30

U S Department of Energy

BETO Project officer Prasad GupteProject Coordinator Cynthia Tyler

Southern ResearchAmit Goyal (PI)Santosh Gangwal (Co-PI)Jadid SamadLindsey ChattertonGovedarica Zora

Cytec SolvayLonggui Tang (Lead)Billy Harmon

NJITZafar Iqbal (Lead)El Mostafa Benchafia

ARBIOMLisette TenlepBill McDonald

RenmatixDan BeacomJeremy Austin

Partners

Sugar Suppliers

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Additional Slides

31

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

S-1

32

F-102

R-101

B1

D-101

F-101

F-103

C-101

B5

S-102

S-103

S-105

S-107

S-108

S-101 S-110

S-111

S-112

S-106

S-113

S-114S-115

S-104

H2 recovery

20 sugar

174 PG(recovery 95)25 EG796 H2O

998 glycerol(recovery 999)

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

R-102

F-104

M-102

D-102

M-101S-119

S-121

S-120S-122

S-123

S-124S-116

S-117 S-118

S-2

33

88 Acrolein(recovery 997)018 Acetol007 Propanal

21 Acetol(recovery 992788 Water

80

gly

cero

l +

H2O

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

S-3

34

R-103

D-103

D-104D-105

S-126

S-127

S-125

S-130

S-131

S-129

S-128

S-133

S-134

S-132

S-135

S-138

S-137

S-136

ACN+AN recycle

ACN(recovery 994)

H2O (l)

Steam AN+H2O

Steam

H2O (l)

AN+H2O

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization

Publications Patents Presentations Awards and Commercialization

PublicationsPresentationsbull Amit Goyal and Santosh Gangwal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon

Fibers Poster Presentation at Bio Pacific Rim Summit Dec 6 to 9 2015 San Diego CAbull Project Fact Sheet for BioEnergy Summit June 23rd ndash June 24th 2015 Washington DCbull Amit Goyal and Santosh Gangwal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon

Fibers Oral Presentation at Bio World Congress July19th - 22nd Montreal Canada Invited talk in Breakout Panel Session Clustered Research and Development of Ag-Based BioProducts

bull DOE Site Visit ndash 15th September 2015 Results for overall progress presented to Program manager and coordinator at Durham NC

bull Amit Goyal Process for Biomass Conversion to Acrylonitrile- Precursor for Production of Carbon Fibers October 5th

2015 Invited Talk at Department of Materials Science at University of Alabama Birminghambull Amit Goyal Jiajia Meng Jonathan P Carroll and Santosh K Gangwal Biomass Conversion to Acrylonitrile Monomer-

Precursor for Production of Carbon Fibers Oral Presentation at AICHE Fall 2015 meeting (579b)bull Amit Goyal Zora Govedarica Lindsey Chatterton and Santosh K Gangwal Acrylonitrile production from non-food

biomass derived sugars for synthesis of carbon fibers Oral Presentation as a Panel Speaker for World Congress on Industrial Biotechnology Breakout Session Process Improvement for Biobased Materials

bull Jadid E Samad and Amit Goyal Non-food biomass to acrylonitrile A cheaper and greener route to automotive grade carbon fibers Poster presentation at BioEnergy Summit July 12-14 Washington DC

bull Jadid E Samad Lindsey Chatterton Zora Govedarica Amit Goyal Thermocatalytic Process for Biomass Conversion to Acrylonitrile for Production of Carbon Fibers Oral presentation at TCS 2016 Chapel Hill NC

bull Amit Goyal Longgui Tang and Billy Harmon Renewable Acrylonitrile for Carbon Fiber Production Oral Presentation at Carbon Fiber 2016 Scottsdale AZ

bull Jadid E Samad Lindsey Chatterton Zora Govedarica and Amit Goyal Biomass Conversion to Acrylonitrile Monomer-Precursor for Production of Carbon Fibers AICHE November 13-18 2016 San Francisco CA

Patents bull US Application 20160368861 Compositions and methods related to the production of acrylonitrilebull US Application 15245835 Compositions and methods related to the production of acrylonitrile 35

• Biomass Conversion to Acrylonitrile Monomer-Precursor for the Production of Carbon Fibers
• • Goal Statement
  • Quad Chart Overview
  • 1 - Project Overview
  • 2 ndash Approach (Management)
  • 2 ndash Approach (Technical)
  • 3- Technical accomplishmentsprogressresults
  • • R1Hydrocracking
    • R2Dehydration
    • Moving forward with PG Alternative Approach
    • R3Ammoxidation
    • ACN validation
    • TEALCA
    • • Preliminary TEA
      • Cost distribution pie charts
      • Sensitivity analysis
      • Preliminary LCA
      • • Technical progress summary
        • • 4 ndash Relevance
          • • Technology Transfer -Initiatives
            • • 5 ndash Future Work
              • Summary
              • Acknowledgements
              • Additional Slides
              • • S-1
                • S-2
                • S-3
                • Publications Patents Presentations Awards and Commercialization