TRENDS IN TECHNOLOGY FOR PRODUCTION OF BIOFUELS AND BIO-DERIVED CHEMICALS

Bio-fuels

Biodiesel and Bio-lubricants

Green Diesel

Alcohols for fuel additives

Jet Fuels

Biodiesel and Bio-lubricants

Biodiesel production increased over 1000% in the past decade

Biodiesel capacity Worldwide in 2012: 5,670 MMgpy

Biodiesel earns $1.50 per gallon under the U.S. RFS program

1st GENERATION BIODIESEL PLANTS

Transesterification

Homogeneous catalysts

Poor Glycerin Quality

High Feedstock Cost

Emissions issues

2nd GENERATION BIODIESEL PLANTS

Transesterification

Heterogeneous catalysts

Difficult Separation of Glycerin

Lower Feedstock cost

High Capital Investment

3rd GENERATION BIODIESEL PLANTS

Hydrolysis followed by Esterification using Catalytic Distillation

Heterogeneous catalysts

Easy separation of high quality Glycerin

Lowest Feedstock cost

Lower Capital Investment

OILFFA

CONTENTRELATIVE

PRICEPRICE(¢ / #)

PFAD (Palm Fatty Acid Distillate) 85-90% Low 27

Beef Tallow: choice prime 5-6% Medium 32

Beef Tallow: Special 10% Medium 30

Beef Tallow: No. 1,2,3 10-35% Low 31

Grease• White A,B• Yellow• House• Brown (trap)

8-10%15%20%50%

MediumMedium

LowLow

32282625

Poultry Fat 30

Algae Oil 4-15% Medium ?

Soybean Oil 2-3% High 39

Biodiesel and Bio-lubricants

FAT

SPLITTING COLUMN

500°F @ 850 PSIG

WATER

STEAM900#

FLASH VESSEL

FL

AS

H V

ES

SE

L

STEAMPV

LV

PV

TV

PV

TV

LV

PV

STEAM

LV

OIL WATER INTERFACE

PRODUCTION OF FATTY ACIDS

PRODUCTION OF BIODIESEL &

BIOLUBRICANTS

25% GLYCERIN

MU

LT

IPL

E E

FF

EC

T

PR

EC

ON

CE

NT

RA

TO

R

CATALYTIC DISTILLATION

COLUMN

350°F @ 200 PSIG

CRUDE FAME CIRCULATION PUMP

CAT. DIST. COLUMN REBOILER

WATER CIRCULATION

PUMP

METHANOL COLUMN REBOILER

METHANOL CIRCULATION

PUMP

FAT CIRCULATION

PUMP

FAME STRIPPING COLUMN REBOILER

FAT CIRCULATION

PUMP

METHANOL COLUMN OVERHEAD CONDENSER

FAME TO TANK FARM

WASTEWATER TO DISPOSAL

TO VACUUM J ETS

METHANOL DEHYDRATION COLUMN

METHANOL COLUMN OVERHEAD RECEIVER

FAME COLUMN OVERHEAD CONDENSER

FAME COLUMN OVERHEAD RECEIVER

FAME STRIPPING COLUMN

FV

FV

FV

LV

LV

LV

LV

METHANOL

Biodiesel and Bio-lubricants

Green Diesel

Considered a drop-in hydrocarbon replacement for Diesel

Earns $1.65 per gallon under the U.S. RFS program

Only a few operational plants currently

•HYDROTREATING – Hydrodeoxygenation•High

hydrogen consumption

•Complicated separations

•Low value side products

•DECARBOXYLATION – Hydro-decarboxylation•Less

hydrogen used

•Some complicated separations, purge loss

•Hydrogen recycle expensive

•HYDROTHERMAL DECARBOXYLATION•No

hydrogen needed

•Simplified separations

SPLITTING TO MAKEFATTY ACIDS

TRANS-ESTERIFICATION

HYDROGENATION15 mols H2/mol

triglycerideParrafinic Biodiesel

LOW TO MEDIUMFATTY ACID

CONTAINING OILS

MEDIUM TO HIGHFATTY ACID

CONTAINING OILS

BIODIESEL/BIOLUBRICANTS

Fatty Acid Methyl Ester Biodiesel

MILD HYDROCRACKING/

ISOMERIZATIONBiojet Fuel

NATURALTRIGLYCERIDES

CATALYTIC DISTILLATION

DECARBOXYLATION1 mol CO2 removed/

mol fatty acidParrafinic Biodiesel

BIODIESEL/BIOLUBRICANTSFatty Acid Methyl

Ester Biodiesel

GLYCEROL

GREEN DIESEL

Catalyst volume will change as a function of catalyst type and whether the catalyst is incorporated within structured catalytic packing or whether the catalyst is conventionally charged

Pilot Plant Reactor Type Volume of Catalyst

Design Pressure

Design Temp.

Liquid Feeds

Gas Feeds Feedstock Product

Transesterification Packed Bed 2,000 ml

100 bar

(1500 psig)

300°C

(575°F)

2 1 Triglycerides Biodiesel / Biolubricants

Green Diesel – Hydrodeoxidation (HDO)

Packed BedMolten Salt Bath Furnace

250 ml

70 bar

(1000 psig)

375°C

(700°F)

1 2 Triglycerides Diesel range parrafins

Catalytic Distillation

Heterogeneous Catalyst Loaded Column

2”x20 ft.

50 bar

(750 psig)

200°C

(400°F)

2 1 Fatty acids Biodiesel / Biolubricants

Catalytic Decarboxylation (CDC)

Packed Bed 5 zone electric

heater50 ml

30 bar

(450 psig)

350°C

(650°F)

1 2 Fatty acids Diesel range parrafins

Hydrothermal Decarboxylation

Packed Bed 5 zone electric

heater50 ml

180 bar

(2600 psig)

350°C

(650°F)

2 0 Triglycerides Green Diesel

Mild Hydrocracking/ Isomerization

Packed bed 5 zone electric

furnace50 ml

100 bar

(1500 psig)

375°C

(700°F)

1 2Biodiesel

range parrafins

Bio-SPK (biojet fuel)

Alcohols for fuel additives

Worldwide ethanol production in 2012: 28,000 MMgpy

10% blend wall reached in US. Projected gasoline consumption 133 billion gallons

Traditional ethanol earns $0.95 per gallon under the U.S. RFS program

1st GENERATION

Corn from ethanol

Food v. fuel debate

Cannot be put in pipeline

Low energy density

(70,000 Btu/gal – 19.6 MJ/L)

Corrosion issues

2nd GENERATION

Cellulosic ethanol

Solves debate

Earns higher credit

Same issues as traditional ethanol

3rd GENERATION

N-Butanol from waste starch or sweet sorghum

Solves debate

Can be put into pipeline

Energy density closer to gasoline

(110,000 Btu/gal – 29.2 MJ/L)

No Corrosion issues

Can be put into diesel as well.

Blend wall is increased to 12%

OPPORTUNITIES FOR N-BUTANOL

More toxic to the organisms. Lower yields make batch process un-economical

Most organisms make iso-butanol

n-butanol is used as a chemical intermediate for the production of a number of valuable chemicals such as: Butyl Acetate, Butyl Acrylate, Glycol Ethers, etc.

Expected to be a 9.4 billion per year market by 2018.

China currently consumes 35% of the n-butanol produced

CHALLENGES FOR N-BUTANOL

Alcohols for fuel additives

AQ

UEO

US

SEPA

RATO

R

FEED FROM FERMENTER

SO

LVEN

T CO

LUM

N

MIXED ALCOHOL

BUTANOL

WATER

100°C 117°C D

ECAN

TER

Solution: Immobolized organism with continuous removal of butanol

Jet Fuels

Current Jet fuel demand is 5 million barrels per day.

Now earns RIN credits of $1.50 - $1.65 per gallon under RFS

Fuel costs are approximately 35 – 45% of an airlines cost. Volatility is damaging.

•HYDROTREATING FOLLOWED BY HYDRO-ISOMERIZATION•Consumes

hydrogen•Second

reactor system

•Complicated separations

•Lowers density of fuel which limits the amount of bio-fuel that can be used (ASTM 7566: 50% max)

•DECARBOXYLATION AND ISOMERIZATION IN ONE STEP.•Less

hydrogen used

•Single reactor train

•Making rings and minimizing cracking increases density of fuel.

Modularity

The concept of modularity for the design of pilot plants, demonstration plants and small commercial plants was pioneered by our group. This concept now has found universal acceptance in terms of maintaining QA/QC controls, assembly procedures and reducing overall project costs .

Aspen Plus Simulation

+Heat & Material

Balances+

Process Flow Diagrams

Process & Instrumentation

Diagrams+

Equipment Specs+

Instrument Specs+

Control Philosophy

Detailed Engineering

+3D Plant Design

Procurement+

Construction+

Field Testing

Phase 1Phase 1 Phase 2Phase 2 Phase 3Phase 3 Phase 4Phase 4

Project Implementation Sequence

Catalyst Research Systems

• The basic requirement in the analysis of catalytic reactors is a rate expression for the reaction concern.

• The choice of a suitable reactor for carrying out experiments under conditions where meaningful kinetic rate expressions can be obtained is of very great importance.

Unitel: Breadth of Application

Catalyst Research

Petro-chemicals

Energy Research

Misc. Unit Operations

Pharmaceutical &

Nutraceutical

PE

Gasification

Petroleum Refining

Polymerization

Environmental

Transesterification

H C O C R1 + CH3 CH2

H O O H

H

MIXED TRIGLYCERIDE +ETHANOL

O C

O

R1

Catalyst

+

ETHYL ESTERS +

H C O H

H C O H

H

H C O H

H

GLYCERINE

H C O C R 2 + CH3 CH2

O O H

H C O C R3 + CH3 CH2

O O H

CH3 CH2

O C

O

R2

CH3 CH2

O C

O

R3

CH3 CH2

=

Green Diesel – HydroDeOxidation(HDO) Pilot Plant

“Green Diesels” consist of diesel-range (C12-C18) paraffins of high cetane numbers

Deoxygenation by hydrogenation of triglycerides

No glycerin byproduct

NiMo catalysts

Hydrotreat/hydrocrack the trigylcerides – remove O (Oxygen) atoms as H2O

Very high hydrogen consumption

Yield = 50-60%

Big H2 plant investment; or incorporated into a refinery

C57H104O6 + 15H2 6H2O + C3H8 + 3 C18H38

triglyceride hydrogen water propane diesel

CO2 + H2 CO + H2O CO + 3H2 CH4 + H2O

CO2 + 4H2 CH4 + 2H2O

The Chemistry – Biodiesels

Catalytic Distillation

Fatty Acids

R1 — C — OH + OH — CH2 — H

O

O

O

Methanol Water Methyl Ester

R1 — C — O — CH2 — H + H2O

O

O

O

R2 — C — O — CH2 — H + H2O

R3 — C — O — CH2 — H + H2O

R2 — C — OH + OH — CH2 — H

R3 — C — OH + OH — CH2 — H

Catalytic DeCarboxylation(CDC) Pilot Plant

Decarboxylation – the critical step towards jet fuel

decarboxylationthe critical step towards jet fuel

R1 — C — OH

O Heterogeneous Catalyst

Fatty Acids

R1H + CO2

ParaffinicHydrocarbon

Carbon Dioxide

∆G (300 C) = -83.5 KJ /mol∆H (300 C) = 9.2 KJ /mol

Heterogeneous Catalyst

R1H

ParaffinicHydrocarbon

n-C17H34

C10-C15

BranchedParaffins

Mild Hydrocracking&

Hydroisomerization

Decarboxylation

Catalytic DeCarboxylation(CDC) Pilot Plant

FATTY ACID FEED

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CARBON DIOXIDE (>30 BAR)

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HYDROGEN(>30 BAR)

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Catalyst charge: 50 mLReactor internal volume: 100 mLMaximum system pressure: 30 bar (~450 psig)Maximum system temperature: 350°C (~650°F)Number of liquid feeds: 1Maximum LHSV of liquid feed: 2Number of gas feeds: 3

2 high pressure, 1 low pressure

FRN-xxxSPLIT TUBE MULTI ZONE FURNACE

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CATALYTIC DECARBOXYLATION PILOT PLANT

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Mild Hydrocracking – Isomerization Pilot Plant

Optimizing the jet fuel

Heterogeneous Catalyst

R1H Paraffinic

Hydrocarbonn-C17H34

C10-C15 Branched

ParaffinsMild

Hydrocracking & Hydroisomerizatio

n

Mild Hydrocracking – Isomerization Pilot Plant

MILD HYDROCRACKING – ISOMERIZATION PILOT PLANT

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CONFIDENTIAL

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Catalyst charge: 50 mLReactor internal volume: 100 mLMaximum system pressure: 100 bar (~1500 psig)Maximum system temperature: 375°C (~700°F)Number of liquid feeds: 1Maximum LHSV of liquid feed: 2Number of gas feeds: 3

(1 high pressure, 2 low pressure)

FRN-xxxSPLIT TUBE MULTI ZONE FURNACE

RX-xxxTUBULAR REACTOR

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Our Current Projects

At the present time, some of the projects that we are working on are strange and interesting. Some examples are:

Recirculating fluidized bed based pyrolysis of biomass to produce pyoil

Monetization of natural gas into methanol using modular construction technologies

Monetization of natural gas into DME using catalytic distillations

Conversion of triglycerides into jet fuels using catalytic decarboxylation and catalytic hydroisomerization

Pilot plant to study and optimize next generation CO2 absorbing technologies

Eight reactor hydrotreating pilot plant

Biomass oxyblown gasification for syngas production

Upgrading of tar sand derived bitumens

Why Pilot Plants?

Commit your blunders on a small scale and make your profit on a large scale.

Pilot and demo plants represent the intermediate state between laboratory studies and industrial plants.

The pilot and demo plant must be understood not as a scale-up of laboratory units but as a small scale simulation of the future industrial plant.

xxx

The objectives of a pilot plant, therefore, can differ depending on the specific circumstances of each project, and the decision for its construction can include one or several of the following objectives:

To optimize the operating parameters of the process,

To study the effects of recirculating process streams and of accumulation of impurities over long periods,

To obtain process information necessary to specify and design the full scale plant,

To test process control systems and procedures,

To test materials of construction,

To optimize the design of the equipment,

To obtain sufficient information to prepare detailed and reliable estimates of capital and operating costs and to prepare a reliable economic evaluation of the project,

To gain operating experience. and to train the personnel that will operate the full scale plant,

To identify hazards in the process and ensure safety in design and operation, including the disposal of radioactive wastes,

To produce a reasonable amount of uranium concentrate for characterization and for use in subsequent stages of the nuclear fuel cycle.