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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


3rd GENERATION BIODIESEL PLANTS
2nd GENERATION BIODIESEL PLANTS

Transesterification
Homogeneous catalysts
Poor Glycerin Quality
High Feedstock Cost
Emissions issues

Transesterification
Heterogeneous catalysts
Difficult Separation of Glycerin
Lower Feedstock cost
High Capital Investment

Hydrolysis followed by Esterification


using Catalytic Distillation

Heterogeneous catalysts
Easy separation of high quality Glycerin
Lowest Feedstock cost
Lower Capital Investment

Biodiesel and Bio-lubricants

FFA
CONTENT

RELATIVE
PRICE

PRICE
( / #)

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%

Medium
Medium
Low
Low

32
28
26
25

OIL
PFAD (Palm Fatty Acid Distillate)

Poultry Fat

30

Algae Oil

4-15%

Medium

Soybean Oil

2-3%

High

39

Biodiesel and Bio-lubricants

HYDROTHERMAL DECARBOXYLATION
No hydrogen needed
Simplified separations
DECARBOXYLATION Hydro-decarboxylation
Less hydrogen used
Some complicated separations, purge loss
Hydrogen recycle expensive
HYDROTREATING Hydrodeoxygenation
High hydrogen consumption
Complicated separations
Low value side products

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

Green Diesel

NATURAL
TRIGLYCERIDES

LOW TO MEDIUM
FATTY ACID
CONTAINING OILS

MEDIUM TO HIGH
FATTY ACID
CONTAINING OILS

SPLITTING TO MAKE
FATTY ACIDS

GLYCEROL

GREEN DIESEL
HYDROGENATION
TRANSESTERIFICATION

BIODIESEL/
BIOLUBRICANTS
Fatty Acid Methyl Ester
Biodiesel

15 mols H2/mol
triglyceride
Parrafinic Biodiesel

DECARBOXYLATION
1 mol CO2 removed/
mol fatty acid
Parrafinic Biodiesel

MILD
HYDROCRACKING/
ISOMERIZATION
Biojet Fuel

CATALYTIC
DISTILLATION

BIODIESEL/
BIOLUBRICANTS
Fatty Acid Methyl
Ester Biodiesel

Reactor Type

Volume of
Catalyst

Transesterification

Packed Bed

2,000 ml

Green Diesel
Hydrodeoxidation
(HDO)

Packed
BedMolten Salt
Bath Furnace

250 ml

Catalytic Distillation

Heterogeneous
Catalyst
Loaded
Column

2x20 ft.

Catalytic
Decarboxylation
(CDC)

Packed Bed 5
zone electric
heater

50 ml

Hydrothermal
Decarboxylation

Packed Bed 5
zone electric
heater

50 ml

Mild Hydrocracking/
Isomerization

Packed bed 5
zone electric
furnace

50 ml

Pilot Plant

Design
Pressure

Design
Temp.

100 bar

300C

(1500 psig)

(575F)

70 bar

375C

(1000 psig)

(700F)

50 bar

200C

(750 psig)

(400F)

30 bar

350C

(450 psig)

(650F)

180 bar

350C

(2600 psig)

(650F)

100 bar

375C

(1500 psig)

(700F)

Liquid
Feeds

Gas
Feeds

Feedstock

Product

Triglycerides

Biodiesel /
Biolubricants

Triglycerides

Diesel range
parrafins

Fatty acids

Biodiesel /
Biolubricants

Fatty acids

Diesel range
parrafins

Triglycerides

Green Diesel

Biodiesel
range
parrafins

Bio-SPK
(biojet fuel)

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

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

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

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

Alcohols for fuel additives

100C

SOLVENT COLUMN

DECANTER

FEED FROM
FERMENTER

AQUEOUS SEPARATOR

Solution: Immobolized organism with continuous removal of butanol

117C

BUTANOL

WATER

MIXED
ALCOHOL

DECARBOXYLATION AND ISOMERIZATION IN ONE STEP.


Less hydrogen used
Single reactor train
Making rings and minimizing cracking increases density of fuel.

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)

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.

Jet Fuels

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 .

Project Implementation Sequence

Phase
Phase 11

Aspen Plus
Simulation

Heat &
Material
Balances

Process Flow
Diagrams

Phase
Phase 22
Process &
Instrumentation
Diagrams

Equipment
Specs

Instrument
Specs

Control
Philosophy

Phase
Phase 33

Detailed
Engineering

3D Plant
Design

Phase
Phase 44

Procurement

Construction

Field Testing

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

Energy
Research

Petrochemicals

Polymerization

Environmental

PE
Petroleum
Refining
Pharmaceutical
&
Nutraceutical

Catalyst
Research

Misc. Unit
Operations
Gasification

Transesterification

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
C57H104O6
triglyceride

+ 15H2
hydrogen

6H2O + C3H8 + 3 C18H38


water

propane

diesel

CO2 + H2 CO + H2O
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O

Very high hydrogen consumption


Yield = 50-60%

Big H 2 plant investment; or incorporated into a refinery

The Chemistry Biodiesels

R 1 C OH + OH CH 2
H
O
R 2 C OH + OH CH 2
H
O
R 3 C OH + OH CH 2
H

Fatty Acids

Methanol

R 1 C O CH 2 H + H 2O
Catalytic
Distillatio
n

O
R 2 C O CH 2 H + H 2O
O
R 3 C O CH 2 H + H 2O

Methyl Ester

Water

Catalytic DeCarboxylation
(CDC) Pilot Plant

Decarboxylation the critical step towards jet fuel

Catalytic DeCarboxylation
(CDC) Pilot Plant

Mild Hydrocracking
Isomerization Pilot Plant

Optimizing the jet fuel

R 1H
Paraffinic
Hydrocarbon
n-C 17H 34

Heterogeneous
Catalyst
Mild
Hydrocracking &
Hydroisomerizatio
n

C 10-C 15
Branched
Paraffins

Mild Hydrocracking
Isomerization Pilot Plant
TI

TE
xxx

xxx

TE
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xxx

TE
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xxx

TE
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xxx

TE
xxx

xxx

TI

TI

PI
PI
xxx

xxx
PT
xxx

PT
xxx

FT
xxx

xxx

PI
xxx

PT
xxx

VENT

FV
xxx

MASS
THERMAL

TSS

FC

FC

TIC
xxx

CK-xxx

PI
xxx

PCV
xxx

TIC
xxx

VENT

FV
xxx

MASS
THERMAL

F-xxx

XV
xxx

XY
xxx

CK-xxx

TSS
xxx
TIC
xxx

xxx

TE
xxx

xxx

XY
xxx

TIC

FC

FC

HV-xxx

TE
xxx

F-xxx

LIC
xxx

TE
xxx
LV
xxx

RX-xxx
TUBULAR
REACTOR

LY
xxx

IA

XV
xxx

xxx
F-xxx

TO GC /
ANALYTICAL

LIT
xxx

FV
xxx

MASS
THERMAL

TSS

IA

VENT

VENT

HV-xxx
TE
xxx

TY
xxx

PSV
xxx

PI
xxx

HS
xxx

KY
xxx

FT
xxx

PCV
xxx

AS
KV
xxx

FRN-xxx
SPLIT TUBE MULTI
ZONE FURNACE

HS

xxx

PI
xxx

FC

TE
xxx

FC

FIC

NITROGEN
(>10 BAR)

TO VENT

VENT

TY
xxx

FC

FC

FQI
xxx

IA

VENT

PSV
xxx

PI
xxx

xxx

xxx

FT
xxx

LOW PRESSURE
H2/H2S ACTIVATION GAS
(>10 BAR)

TE
xxx

TY
xxx
TSS

HS

xxx

FQT
xxx

FQI-xxx

F-xxx

CK-xxx

F-xxx

FIC

IA

VENT

FO

TY
xxx

XY
xxx

xxx
F-xxx

PV
xxx

E
IA

XV
xxx

PCV
xxx

PY
xxx
PSV
xxx

PCV
xxx

S
VENT

PSV
xxx

PCV
xxx

PI
xxx

PT
xxx

xxx

PI

xxx

PI
xxx

PI
xxx

HS

xxx

HIGH
PRESSURE
HYDROGEN
(>100 BAR)

PI
xxx

TI

VENT

FIC
PI

PSV
xxx

TI

TE
xxx
TE
xxx

CK-xxx

TY
xxx
PI
xxx

PCV
xxx

TSS
xxx
TIC

VENT

xxx
Set at xxx bar

ALKANE FEED

HS
xxx

TIC

M
xxx

TE
xxx

xxx

WAL

V-xxx
FEED TANK

HTR
xxx

WI
xxx

DRAIN

Catalyst charge: 50 mL
Reactor internal volume: 100 mL
Maximum system pressure: 100 bar (~1500 psig)
Maximum system temperature: 375C (~700F)
Number of liquid feeds: 1
Maximum LHSV of liquid feed: 2
Number of gas feeds: 3
(1 high pressure, 2 low pressure)

PT
xxx

HS
xxx

E
HV-xxx

CK-xxx

V-xxx
HYDROISOMERIZED
PRODUCT RECEIVER

HV-xxx
DRAIN

WT
xxx
HV-xxx

xxx
PI
xxx

PI
xxx

TY
xxx

TE
xxx

PI

PSV
xxx

xxx bar

HV-xxx

WAH

TE
xxx

HV-xxx

P-XXX
DIAPHRAGM
METERING FEED
PUMP

CONFIDENTIAL
WAH

HV-xxx
F-xxx

WAL

WI
xxx

411 Business Center Drive, Suite 111


Mt. Prospect, IL 60056 USA
www.uniteltech.com

WT
xxx

HV-xxx

HYDROISOMERIZED
PRODUCT

MILD HYDROCRACKING ISOMERIZATION


PILOT PLANT
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Project No.:
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Drawn by:
JAB

Rev No.:
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Date:
8/26/10

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 CO 2 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.