distributed bio-oil reforming - us department of...

Distributed Bio-Oil Reforming2006 DOE Hydrogen, Fuel Cells & Infrastructure

Technologies Program Review

R. J. Evans, S. Czernik, R. French, J. Marda

National Renewable Energy LaboratoryMay 16, 2006

This presentation does not contain any proprietary or confidential information

Project ID#PD5

Disclaimer and Government License

This work has been authored by Midwest Research Institute (MRI) under Contract No. DE-AC36-99GO10337 with the U.S. Department of Energy (the “DOE”). The United States Government (the “Government”) retains and the publisher, by accepting the work for publication, acknowledges that the Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for Government purposes.

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OverviewTimeline• Project start 2005• Project end 2010• 15% completed

Production BarriersA. Fuel Processor Capital B. Fuel Processor ManufacturingC. Operation & MaintenanceD. Feedstock Issues F. Control & Safety

Target $3.60/gge

Budget• FY05 $100K• FY06 $300K

Partners• Colorado School of Mines (FY06) - Oxidative cracking• Chevron (FY06) - Feedstock Project planned for FY06

ApproachBio-oilPYROLYSIS

REFORMING

Biomass Methanol

H2

Show that bio-oil and blends with methanol can be fed without excessive cokingand develop a process to meet HFC&IT cost and performance objectives.

VOLATILIZATION

O2 Low TemperatureOxidative Cracking

SHIFT

SEPARATION

H2O

CO2

Objectives

• Overall: – Develop the necessary understanding of the

process chemistry, compositional effects, catalyst chemistry, deactivation, and regeneration strategy as a basis for process definition for automated distributed reforming

• FY06– Demonstrate partial oxidation and show that it can

reduce the required catalyst loading in the reforming step by 50%

Distributed Bio-Oil Reforming Approach

Volatilization Oxidative Cracking

Bio-Oil (+MEOH) O2

Catalytic Auto-Thermal H2

Enabling Research:

Process Integration:

H2O

Oxidative Cracking Kinetics and Mechanisms

Process Optimization

Catalyst Screening

Low Temperature Catalytic Oxidation Mechanisms

Engineering Testing

AirIndirect Heat

Heat and Mass Balance

H2O, CO, CH4,CO2

Separation

H2O + CO2

~400oC ~650oC

Q

Technical Accomplishments

• FY05: Whole oil successfully run– With 10% MeOH addition, bio-oil

processing was trouble free over short run durations (up to 16 hrs)

• FY06: Accomplishments to date– Bio-oil volatilization method developed– Oxidative cracking promising results – Progress toward July milestone on target

Thermal Severity

Primary Secondary Tertiary

Biomass H2OCOCO2

Char

“Carbon”

Bio-Oil H2OH2CH4COCO2PAH

H2, CO, CO2, H2O, C2H4,+Furans, Phenols, BTX, Ketenes, Olefins…

HC

O

CH2HO

OH

OH

Equilibrium Modeling Results

O0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

C

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

H

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

650 oC

550 oC

P = 1 atm

CarbonDeposition

No CarbonDeposition

12 3

4 5 6 78

910111213

14

15161718

19

2021

2223

1 = Bio-Oil composition, which liesin the region where carbon will form at 650 C

2-8 = O2 addition points9-13 = H2O addition

14-23 = both O2 and H2O

Goal is to identify the thermodynamic and kinetic domains for deposit free operation

Spray Injector Reactor System

Spray Injector Results

Run Liq. Feed

g/minAir coeff.

% Temp, C Time, s N2 O2 H2 CO CO2 CH4 C Bal, %1 0.5 163 600 2.4 79 15.96 0.00 1.19 4.19 0.00 76%2 0.5 162 599 1.1 78 17.18 0.00 0.59 4.16 0.00 68%3 1.0 99 602 1.4 79 11.61 0.00 2.78 6.26 0.00 69%4 1.0 65 601 1.5 79 5.27 0.00 4.06 11.64 0.00 65%5 1.0 66 636 1.4 80 2.28 0.00 5.96 11.74 0.08 74%6 1.0 59 650 1.4 78 0.95 0.82 6.92 13.36 0.23 71%7 1.0 53 649 1.4 75 0.48 1.45 11.05 11.27 0.40 65%8 1.0 47 650 1.4 72 0.24 3.24 14.75 9.33 0.72 56%9 1.0 34 647 1.4 29 0.19 22.11 32.11 15.38 1.63 32%

10 0.9 54 698 1.3 73 0.13 2.56 12.52 10.94 0.63 70%11 1.0 52 748 2.9 68 0.00 6.55 13.20 11.21 1.26 76%12 1.0 54 750 2.7 75 0.03 3.92 9.05 11.23 0.74 72%

Gas Composition, vol. %

Spray injection resulted in low carbon conversionto CO and formation of aromatics and carbon

Schematic of Pyrolysis Reactor & NREL’s MBMS Sampling System

MolecularDragPump

CollisionsQ1 Q2 Q3

ArgonCollision

Gas

TurbomolecularPump

TurbomolecularPump

TurbomolecularPump

ProductsandTransients Three Stage Free-Jet

Molecular Beam SourceTriple QuadrupoleMass Analyzer

{P+} {D+}

Detector

e-

EISource

He

He

Tpy

T1 T3 T4 T5

He

T2

Bio-Oil Film Volatilization – 400 oC

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 0.25 0.5 0.75 1

Time, Min.

Dife

rent

ial S

igna

l, %

of t

otal

0

25

50

75

100

Inte

grat

ed S

igna

l,% o

f tot

al

46 mg

51 mg

54 mg

Average Residue = 6%

Bio-Oil Film Volatilization MBMS Bio-Oil Spectrum

Toil = 300 oC Tvc = 300 oC no O2

31

272

164

137

60

43

18

0

1

2

3

4

5

0 25 50 75 100 125 150 175 200 225 250 275 300

m/z

% o

f Tot

al Io

n Si

gnal

HC

O

CH2HO

CH3

OH

OMeO

O

HO

Bio-Oil Film Volatilization Cracking 0.5 s @ 650 C

Toil = 400 oC Tvc = 650 oC no O2

124136

110

28

31

60

43

18

0

1

2

3

4

5

6

7

0 25 50 75 100 125 150 175 200 225 250 275 300

m/z

% o

f Tot

al Io

n Si

gnal

OH

OH

OH

CHO

CH3

Bio-Oil Film VolatilizationOxidative Cracking 0.5 s @ 650 C

44

11060

18

0

5

10

15

20

25

0 25 50 75 100 125 150 175 200 225 250 275 300

m/z

% o

f Tot

al Io

n Si

gnal

Toil = 400 oC Tvc = 650 oC with O2

256240226212

198162

144

122

110

0.00

0.10

0.20

0.30

0.40

0.50

0.60

100 125 150 175 200 225 250 275 300

H2O

CO

CO2

Ultrasonic Nozzle

• Generating a fine mist at 0.3g/min

• Enables steady liquid feed at low rates

Dual Syringe Pump

Bio-Oil

Water

Power Supply

Gas MFM

MBMS

Ultrasonic Nozzle

Furnace

Catalyst Bed

Temperature Read-Out

Gas MFM

Ultrasonic NebulizerOxidative Cracking 0.5 s @ 650 C

0.0E+00

5.0E+07

1.0E+08

1.5E+08

2.0E+08

2.5E+08

3.0E+08

3.5E+08

0 2 4 6 8 10 12 14

Time, min

Abu

ndan

ce

18324428

0.0E+00

1.0E+08

2.0E+08

3.0E+08

4.0E+08

10 10.5 11 11.5 120.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

28

44

1878

32

% Residual Carbon: 7.7%

Ultrasonic NebulizerThermal Cracking 0.5 s @ 650 C

15013677

1109460

43

18

0

1

2

3

4

5

6

0 20 40 60 80 100 120 140 160 180 200

m/z

% o

f Tot

al S

igna

l

31 = 13.4%32 = 8.8%

OHCHO

CH3

OH

OH

OH

CH3 C

O

H

HC

O

CH2HO

Ultrasonic NebulizerOxidative Cracking 0.5 s @ 650 C

31

18

28

44

7894 128 178

0

5

10

15

20

25

30

35

40

0 20 40 60 80 100 120 140 160 180 200

m/z

% o

f Tot

al S

igna

l

OH

CO2

CO

H2O

78

94 128

178

00.5

11.5

22.5

33.5

4

75 125 175

MeOH

Carbon ConversionOxidative Cracking 0.5 s @ 650 C

Equil. COEquil. CO2

0

20

40

60

80

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3

O/C Mole Ratio

Car

bon

Con

vers

ion,

%

CO-Bio-Oil/MeOH

CO-MeOH

CO2-Bio-Oil/MeOH

CO2-MeOH

CO-Bio-Oil/MeOH/H2O

CO2-Bio-Oil/MeOH/H2O

CO-Bio-Oil/MeOH/(H2O)*

*H2O not included in O/C

Project Timeline

Task 2: Distributed Reforming of Renewable Liquid Feedstocks

Distributed Reforming

FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012

P2 P5F2 C12

5P6Sf3 C5 A1 A2 Sf5V9

C3

P3 4

Milestones

4 Verify feasibility of achieving $3.60/gge for renewable liquids distributed reforming.5 Down-select research for distributed production from bio-derived renewable liquids.

Outputs

P2 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.P3 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P5 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P6 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.

Inputs

C3 Input from Codes and Standards: Preliminary Assessment of Safety, Codes and Standards requirements for the hydrogen delivery infrastructure.

Sf3 Input from Safety: Safety requirements and protocols for refueling.C5 Input from Codes and Standards: Completed hydrogen fuel quality standard as ISO Technical Specification.A1 Input from Systems Analysis: Complete technoeconomic analysis on production and delivery technologies currently

being researched to meet overall Program hydrogen fuel objective.F2 Input from Fuel Cells: Research results of advanced reformer development.V9 Input from Technology Validation: Final report on safety and O&M of three refueling stations.A2 Input from Systems Analysis: Initial recommended hydrogen quality at each point in the system.C12 Input from Codes and Standards: Final hydrogen fuel quality standard as ISO Standard.Sf5 Input from Safety: Safety requirements and protocols for refueling.

Task 2: Distributed Reforming of Renewable Liquid FeedstocksTask 2: Distributed Reforming of Renewable Liquid Feedstocks


FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012

P2 P5F2 C12


C3

P3 4

Milestones


Outputs


Inputs





FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012FY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012

P2 P5F2 C12


C3

P3 4

Milestones


Outputs


Inputs




Project TimelineTask Name

Bio-Oil VolatilizationProcessing OptionsModification and CharacterizationInjector DevelopmentCoking StudiesGo / No Go on Bio-Oil performance

Oxidative CrackingProof of ConceptReduce Catalyst Loading by 50%Partial Oxidation DatabaseModeling and OptimizationJon Marda Thesis

Catalytic Auto-Thermal ReformingCatalyst Development

Integrated SeparationConcept EvaluationMembrane SupportIntegrated Laboratory System ExperimentGo / No Go on Conceptual Design

Systems Engineering Oxygen, Steam and Heat IntegrationEngineering Design and ConstructionPrototype System DevelopedHeat and Mass BalancesProcess UpsetsLong Duration RunsDemonstrate Distributed Hydrogen Production fromBio-Oil for $3.6/gge

Safety AnalysisReview and Analysis of Pressure, O2, H2Systems Integration

5/31

6/30

5/30

6/1

6/30

12/3

2005 2006 2007 2008 2009 2010 2011

Future Work• FY06

– July milestone: Oxidative cracking proof of concept• FY07

– Catalyst testing and collaborative development for this new approach with emphasis on deactivation and poisoning

– “Go/no go” on bio-oil performance– Kinetic modeling and process optimization– Reaction engineering

• FY08– Bench scale bio-oil reforming tests for long-term testing– Prototype design– “Go/no go” on conceptual design

• FY09– Scale up system development

• FY10– Long duration runs

SummaryRelevance Near Term Renewable Feedstock

for Distributed ReformingApproach Bio-Oil Processed at Low Temp

Homogeneous and Catalytic Auto-Thermal Reforming

Accomplishments Progress in Volatilization and Oxidative Cracking

Collaborations •Colorado School of Mines•Chevron

Future Work •Low Temperature Oxidative Cracking Proof of Concept in FY06•Catalysis in FY07

Response to Reviewers Comments• Project would benefit from commercial and

university collaborations – Work to date has been proof of concept – Collaboration began in FY06 with School of Mines

on modeling and Chevron on feedstock effects– Discussions with UMN on catalysis and GE on

prototype development in progress• More detailed collaborative research plan needed

– Elements are in the plan, pending budget• Bio-feed variation effects• Oxidative cracking kinetics• Catalytic oxidation mechanisms • Factor interactions• Catalyst development

Publications and PresentationsCzernik, S. and French, R., Production of Hydrogen from

Plastics by Pyrolysis and Catalytic Steam Reforming, Energy & Fuels, 2006, 20, 754-758

Czernik, S., Evans, R., and French, R., Hydrogen from Biomass; Distributed Production by Steam Reforming of Biomass Pyrolysis Oil, 1st International Symposium on Hydrogen from Renewable Resources, 231 ACS National Meeting, Atlanta, GA, March 26-30, 2006

Critical Assumptions and Issues

• Bio-Oil Volatilization• Oxidative Homogeneous Cracking

Performance & Benefits• Catalyst Design and Performance• Carbon Deposit Removal and Catalyst

Regeneration Management• Process Energy• Hydrogen Separation

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