© 2006 UOP LLC. All rights reserved.

Challenges in the Exploration of Renewable Energy

Joseph KocalUOP LLC

July 15, 2008

© 2008 UOP LLC. All rights reserved.UOP 4926-01

Outline

• Background• 1ST Generation Renewable Fuels

- Natural oils and fats • 2nd Generation Renewable Fuels

- Lignocellulosics- Algae

• Summary

Inedible Oils: Camelina, Jatropha

Fuel Additives / Blends Fuels

Where is Biofuels Technology Headed?

JetDiesel

UOP’s Bio-Fuels Technology GoalsIdentify and utilize processing, composition, and infrastructure

synergies to lower capital investment, minimize value chain disruptions, and reduce investment risk.

BiodieselEthanol

• Lignocellulosic biomass to fuels

• Algal oils to fuels

Generation 1• Vegetable oils to

diesel, gasoline and jet fuel

Generation 2

Gasoline

UOP 4913C-09

Feed Process Product

Green OlefinsVegetable Oil Green GasolineCatalytic

Cracking

H2 Green DieselVegetable Oil

EcofiningTM

BiodieselGlycerol

BiodieselMethanol

Vegetable OilBiodiesel

Green Chemicals

Lignocellulosic Waste

Green FuelsUpgrading

H2 Green JetVegetable Oil

Refining

UOP 4856I-11

Biomass Processing Routes

Green Diesel vs. Biodiesel (FAME)Veg Oil/ Grease

+ Glycerol

Biodiesel (FAME) Green Diesel

+ Propane

HydrogenMethanol

Petroleum ULSD

Biodiesel (FAME) Green Diesel

Oxygen Content, % 0 11 0Specific Gravity 0.84 0.88 0.78Sulfur content, ppm <10 <1 <1Heating Value MJ/kg 43 38 44Cloud Point, °C -5 -5 to +15 -30 to -10Cetane 40 50-65 70-90Lubricity Baseline Good BaselineStability Baseline Poor Baseline

UOP/ENI EcofiningTM Process to Produce Green DieselUOP 4856I-12

Breakeven Analysis: Sensitivity to Feed Oil Prices

UOP 4856I-13

-$1,400

-$1,200

-$1,000

-$800

-$600

-$400

-$200

$0

$200

$400

Crude Price, $/bbl

$400/MT ($59/bbl)$600/MT ($88/bbl)$800/MT ($118/bbl)$1000/MT ($146/bbl)

Sensitivity to Vegetable Oil Price

NPV

, $M

$25 $35 $45 $55 $65 $85 $95 $105 $115 $125$75$30 $40 $50 $60 $70 $80 $90 $100 $110 $120

Economics Driven by Relative Cost of Feedstocks

DARPA-funded Project for Renewable JP-8 production

UOP 4788H-30DARPA, Project W911NF-07-C-0049

Dr. Douglas Kirkpatrick

Overall Program Objective

1. Demonstrate a process for conversion of natural oils and fats to on-spec JP-8 that is technically and economically feasible

2. Identify viable technology to increase volume and reduce cost of renewable-oil crops

Producing jet-range fuel from deoxygenated natural oils and fats

60 400 500 650 1000 1300Boiling Point, DegF

Gasoline Diesel No. 2 Lubricating Oils Asphalt

Jet

300

Heavy Fuel Oils

1 6 8 10 15 20 43 71Number of Carbon Atoms

5 18 75 4,000 366,000 >1000 TrillionNumber of Paraffin Isomers

Gases

Crude Oil

Deoxygenated Soybean Oil

Deoxygenated Coconut Oil

to JP-8

5-10 11 12 13 14 15 16 17 18 19+Coconut Oil 15 49 18 8 11 0Soybean Oil 0 0 0 11 88 0Deoxygenated Coconut oil 15 19 29 7 11 3 5 4 6 0Deoxygenated Soybean oil 0 0 0 0 0 4 7 35 53 0

Carbon Chain Length

EcofiningTM

Oil Isomerization

Production of Jet Fuel

New Bio-Oil to JP-8 Process Based on Existing UOP Technology

Deoxygenation Green Diesel

Oil Selective Cracking/IsomerizationDeoxygenation Green Jet

UOP 4788H-30

Selective cracking: Process and catalyst development to maximize economic production of

higher yields of jet-range paraffins

Maximizing jet fuel production: Identifying best catalyst through combinatorial chemistry

Combi Catalyst

Preparation

Combi testing

Lab Scale Preparation

Lab plant test/ confirmation

of combi results

Candidates for

development

Variables screened:•Acid supports•Metal type/concentration•Process Variables

g scale 500g scaleModelfeed

DeOx natural oil feed

Pilot plant screening: Yield confirmations/

short term stability

referenceGood performers

Poor performers

Many catalysts

6-8 candidates

Jet r

ange

Cracking Severity

•>70 supports•>2000 final catalysts (with metals)

9 months

Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)

Properties of UOP’s Bio-Based JP-8

SampleFreeze Point,

oC Flash Point, oC Density, g/ccJP8 Spec -47 38 0.775UOP JP-8 range paraffins -52.6 53 0.759†

†Aromatic additives required to make JP-8 specification; also true for synthetic jet fuel

2 samples from different biofeedstocks met JP-8 specifications

JP8 SpecSoybean oil derived JP-8

Coconut oil derived JP-8

Petroleum JP-8

% aromatic (*added) max 25 vol % 15%* 22%* 18.8Freeze Point, C -47 -50 -62 -50Flash Point C 38 54 56 51Specific Gravity @ 15 C .775-.84 0.779 0.780 0.804Heat of combustion (Btu/lb) 18400 min 18600 18655 18600IBP C (D86) 165 169 15910% (D86) 157-205 176 177 18220% (D86) 180 179 18950% (D86) 168-229 199 188 20890% (D86) 183-262 268 226 244FBP C (D86) 300 279 262 265

Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)

Meeting JP-8 specifications: Aromatics to meet density specs

Oil Selective Cracking/IsomerizationDeoxygenation

Green Jet-range

paraffins

UOP 4788H-30

Renewable JP-8

Aromatics(<25%)

Sources of Aromatics• Refinery sources

- Aromatics complexes- Platforming

• Renewable sources- Deoxygenated pyrolysis

oil

BiofuelsSustainability

UncompromisedProduct Quality

Life Cycles

Emissions

Vehicle Fleet

Technology

LignocellulosicCost

Net EnergyProduction ≤Consumption

Efficiency

Supply Chain

Algal

Energy Content

Distributed

FeedstockAvailabilityWorld Trade

Standards

Reduction inClimate Active

CO2 Equivalents

Sustainability

Uses Sustainable Feedstock Source

Established Technology

Supply Chain Issues Addressed

Minimizes Infrastructure Investment

Fleet Compatibility

Cost Neutral or Profitable Within The Fuel Pool

Allows Bio-component Substitution

Sustainability Scorecard

Renewable Fuels: Unlocking the Potential

XX

UOP 4856I-22

Inedible Oils: Camelina, Jatropha

Fuel Additives / Blends Fuels

Where is Biofuels Technology Headed?

JetDiesel

UOP’s Bio-Fuels Technology GoalsIdentify and utilize processing, composition, and infrastructure

synergies to lower capital investment, minimize value chain disruptions, and reduce investment risk.

BiodieselEthanol

• Lignocellulosic biomass to fuels

• Algal oils to fuels

Generation 1• Vegetable oils to

diesel, gasoline and jet fuel

Generation 2

Gasoline

UOP 4913C-09

Relative Heat Content

Source: EIA

(Mill

ion

Btu

/Sho

rt to

n) 25

30

20

15

10

5

0Pet

CokeCoal Pulp &

PaperWaste

Wood/WoodWaste

Muni-cipalSolidWaste

Agri-cultural

by-products

SludgeWaste

Biological feedstocks have lower heat content than fossil feedstocks

UOP 4913C-15

Lignocellulosic Biomass to Fuels Via Pyrolysis

StabilizationPyrolysisBiomass

Mixed Woods

Corn Stover

Deoxygenate

GasolineDieselJetChemicals

Other Refinery

Processes

Biocrude

Refin

ery

P P

P P

P P

UOP 4913C-17Collaboration with DOE, NREL, PNNL

Typical Fast Pyrolysis Process

Biomass

Char

Heat for Drying

Heat for Pyrolysis

Gas

Gas RecycleFluidizingGas

PyrolysisOil

From “Fast Pyrolysis of Biomass: A Handbook.” A.V. Bridgwater et al.

H2O= 10-40%

H2O= 5%

H2O= 15-40%

Reactor

Cyclone

Grind

Dry Cooland

Collect

UOP 4913C-18

Hydrocarbon product rich in cyclic hydrocarbons:product can produce gasoline, jet fuel, diesel, and

chemicals

Deoxygenated Product PropertiesBiofuel

(from mixed wood)

Conventional(from petroleum)

Min Max Gasoline Typical

ULS Diesel Typical

Paraffin, wt% 5 1044 10-60

Limited by cold flowIso-Paraffin, wt%

17 25

Olefin, wt% 0.6 0.9 4 Nil

Naphthene, wt%

40 55 7 10-80

Aromatic, wt% 10 35 38 35 maxLimited by emissions

Oxygenate, wt%

0.1 0.8 Nil Nil

UOP 4913C-19

Deoxygenated Pyrolysis Oil to Jet Fuel

Range of jet range hydrocarbons: 45 – 65% depending on feed source and process conditions

Boiling Point Distribution

0.0

2.0

4.0

6.0

8.0

10.0

0 50 100 150 200 250 300 350 400 450 500 550 600Temperature, °C

wt%

in 1

0° D

elta

T

Mixed Wood Derived (Cond. 1) Mixed Wood Derived (Cond. 2)Corn Stover Derived (Cond. 1) Corn Stover Derived (Cond. 2)

2nd generation Renewable Jet Fuel from oils and biomass

Green Jet-range paraffins

Selective Cracking/

Isomerization

Natural Oils and

FatsDeoxygenation

UOP 4788H-30

Renewable Jet Fuel

Biomass contribution can be >50%

Solid Biomass

Catalytic Stabilization/

DeoxygenationPyrolysis

Jet Range cyclic

hydrocarbons

Renewable Aromatics

JP-8 Spec

StartingParaffin

Deoxygenated Pyrolysis Oil (Corn Stover derived)

Deoxygenated Pyrolysis Oil (Mixed wood derived)

Freeze Point (oC) -47 -53 -56 -54

Flash Point (oC) 39 53 49 54

Density (g/mL) 0.775 0.759 0.790 0.782

100% Bio-derived JP-8 product is possible

Distribution Statement "A" (Approved for Public Release, Distribution Unlimited)

2nd generation Renewable Jet Fuel from algae

Source: Q. Hu,

• High cellular oil content (~50% of dry weight) • High photosynthetic efficiency (10~20%)• Excellent CO2 capture and sequestration capability• Water requirement: less than 1/40 of land plants and thrive

in saline/brackish/waste water• Land requirement: desert and arid lands

Integrated Algal Processing for jet fuel production

CO2

Green Jet (paraffin-rich)Other Products: Green diesel and chemicals

Green Jet (rich in cyclic hydrocarbons)Other products: Green gasoline; diesel; chemicals

2nd Generation On-spec

Renewable Jet Fuel

BiofuelsSustainability

UncompromisedProduct Quality

Life Cycles

Emissions

Vehicle Fleet

Technology

LignocellulosicCost

Net EnergyProduction ≤Consumption

Efficiency

Supply Chain

Algal

Energy Content

Distributed

FeedstockAvailabilityWorld Trade

Standards

Reduction inClimate Active

CO2 Equivalents

Sustainability

Uses Sustainable Feedstock Source

Established Technology

Supply Chain Issues Addressed

Minimizes Infrastructure Investment

Fleet Compatibility

Cost Neutral or Profitable Within The Fuel Pool

Allows Bio-component Substitution

Sustainability Scorecard

Renewable Fuels: Unlocking the Potential

X

X

UOP 4856I-29

Summary

• 1st generation renewable processes commercialized or in development: Natural oils and fats to diesel and jet fuel

• 2nd generation renewable fuel: Biomass and algae to fuels- Proof of principle work completed in NREL-PNNL-UOP

CRADA: Biomass to fuel via pyrolysis oil hydrodeoxygenation

- Algae offers great potential to produce large quantities of oils and biomass for sustainable jet fuel production

Acknowledgements

• NREL - Richard Bain- David Hsu

• PNNL - Doug Elliott - Don Stevens

• UOP - Mike McCall- Tim Brandvold- Graham Ellis- Zhihao Fei- Chris Gosling - Tom Kalnes - Peter Kokayeff- Rich Marinangeli- Terry Marker - Prabhakar Nair

DOE, Project DE-FG36-05GO15085Paul Grabowski

UOP 4913C-28

DARPA, Project W911NF-07-C-0049Dr. Douglas Kirkpatrick

UOP 4926-28