Biomass Energy Delivery through Pyrolysis Oil Anjan Ray UOP India Pvt Ltd Indian Institute of Chemical Engineers December 18, 2010 Gurgaon, India UOP 5363-01.

Biomass Energy Delivery through Pyrolysis OilBiomass Energy Delivery through Pyrolysis Oil

Anjan Ray UOP India Pvt Ltd

Anjan Ray UOP India Pvt Ltd

Indian Institute of Chemical EngineersDecember 18, 2010

Gurgaon, India

UOP 5363-01© 2010 UOP LLC. All rights reserved.

UOP Overview

• Leading supplier and licensor of processing technology, catalysts, adsorbents, process plants, and technical services to the petroleum refining, petrochemical, and gas processing industries.

• UOP Technology Furnishes: 60% of the world’s gasoline; 85% of the world’s biodegradable detergents; 60% of the world’s para-xylene.

• 3400 employees worldwide.

• Strong relationships with leading refining and petrochemical customers worldwide.

• UOP’s innovations enabled lead removal from gasoline, the production of biodegradable detergents, the first commercial catalytic converter for automobiles.

Biofuels: Next in a Series of Sustainable Solutions

2003 National Medal of Technology Recipient

Source: IEA, 2008

Macromarket Summary: Through 2020

Global energy demand is expected to grow at CAGR 1.6%. – Primary Energy diversity will become increasingly important over this

period with coal, natural gas & renewables playing bigger roles Fossil fuels will continue to supply ~80% of primary energy and

90 to 95% of liquid transportation needs Biofuels are expected to grow at 8-12%/year to ~3.0 MBPD

Source: Lux Research, Inc. 2010

Energy Security, GHG Abatement & Economics will Drive Investment

Can bio-based productsreplace petroleum’s…

Physical properties?Versatile and

high-performanceCost?

$12/GJ (@$75/bbl)Scale?

31,000,000,000 bbl/yr

• For which petroleum-based products can bio-based ones directly substitute?

• Can modifications of process or product improve indirect substitution?

• Can technological innovation lower the cost of individual steps?

• Can economies of scale lower the end cost to a competitive level?

• Is there sufficient land area?

• Is the land area productive enough?

UOP 5363-03

Biofuels: Regional Drivers

Drivers Change Priority for Different Economies/Geographies

SE ASIA/ S. AMERICA

• Agro sector focus EUROPE• Energy Security: RED• Global warming: RED/FQD

N. America• Energy Security: RFS• Environment• Agro sector subsidies

AFRICA•Rural developmentCHINA/INDIA

•Energy Security •Rural development•Employment

Biofuels Overview: Technology Pathways

Current biofuel market based on sugars & oils. Use bridging feedstocks to get to 2nd Generation Feeds:

Algae & Lignocellulosics

Transesterification

Enzyme Conversion

Fermentation

C6 Sugars

Dehydration

Acid or Enzyme Hydrolysis

Gasification

Pyrolysis/Thermal

DepolymerizationLights

CO2

Feedstocks Products

Syngas

Direct Conversion

H2O

FCC

Hydrotreating

Bio-oilHydrotreating

FischerTropsch

-

Alcohol Synthesis

Distiller’s Grain

Glycerine

Starches

Natural Oils

GreenGasoline

Ethanol

FAME or FAEE

GreenDiesel/Jet

C5 / C6Sugars

Co-Feed

Lignin, Cellulose & Hemicellulose

Sugars

2nd Gen Feeds(Jatropha,

Camelina & Algal)

RenewableEnergy

= UOP Areas

Petroleum Refining Context

Refining: ~100 years

~750 refineries

~85M BBL of crude refined daily

~50M BBL transport fuels

Complex but efficient conversion processes

High quality transport fuels

Massive ScaleTechnology Evolution Expected

Pro

du

ct T

reat

ing

Ble

nd

ing

Fuel Gas

GasolineJet

Diesels

HeatingOils

Geases

Fuel Oil

LPG SolventsFuels

Lube Oils

Asphalts

Lube OilProduction

Hydrogen Production/Purification/Recovery

Gas-to-Liquids

Natural Gas

Fuel, Wax

Natural Gas, Fuel Oil

H2

Plant Upgrades& Revamps

Plant Maintenance/

Reliability/Safety

EnergyConservation &

Management(Power

Production)

EnvironmentalControls

SolventExtraction &Deasphalting

Gas OilHydrotreating

Light DistillateHydrotreating

Heavy DistillateHydrotreating

NaphthaHydrotreating

Light OlefinsProduction

AromaticsProduction BTXH2

H2

H2

Vacu

um D

istil

latio

n

VisbreakingVacuum Resid

Diesel

Gas Oil

Lube Oils

Heavy Fuel OilAsphalt

Syngas/Steam

ElectricityCoke

Kerosene and Jet Fuels

Diesel and Heating Oils

Gasoline, Naphtha, Middle Distillates, Gasoline

Gasoline

Distillates

Reformate

Diesel and Heating Oil

Fluid CatalyticCracking

Hydrocracking

Cru

de O

il D

istil

latio

n(T

oppi

ng)

Heavy Distillate

Light Distillates

H2

Naphtha

H2

AtmosphericGas Oil

H2

CatalyticReforming

H2

Etherification

Gas ProcessingUnit

Light Ends

Light NaphthaIsomerate

LPG

Sulfur Plant Sulfur

Iso-octaneProduction

Gasification

Iso-octane

Crude Treating& Desalting

Crude Oil

Latest RefiningTechnology

Development & Licensing

Butane-Butylene

Alcohol Isobutane

Butane

Alkylation

Alkylate

Flue Gas

Isomerization

Coking

UOP 5363-04

Biofuels in Modern RefineryContext: Key Attributes

• Supplement crude diet with locally sourced feeds• Provides some insulation against price shock

• More secure supply chain

• Critical issue is creating a truly fungible product• Use the same infrastructure as oil refining today

• Does not require modifications to transport platform

• Address the environmental pressures of fossil fuel combustion• Life Cycle Analysis of biofuels shows dramatic benefits

• Sustainable feed and product chain to insure long term success

• Cost competitive technology offerings

UOP 5363-05

UOP Renewables Vision• Building on UOP technology and expertise• Produce real fuels instead of fuel additives/blends• Leverage existing refining/ transportation infrastructure to lower

capital costs, minimize value chain disruptions, and reduce investment risk.

• Focus on path toward second generation feedstocks & chemicals

Inedible Oils: Camelina, Jatropha

Lignocellulosic biomass,

algal oils

Second Generation

Oxygenated Biofuels

BiodieselEthanol

Hydrocarbon Biofuels

JetDiesel Gasoline

FirstGeneration

Natural oils fromvegetables and

greases

UOP 5149-08

Transition Option

UOP/ENI Ecofining™

Superior technology that produces a drop-in diesel

Uses existing refining infrastructure, can be transported via pipeline, and can be used in existing automotive fleet

CFPP and Cloud Point can be controlled

Excellent blending component, allowing refiners to expand diesel pool by mixing in “bottoms”

Can be used as an approach to increase refinery diesel output

Petrodiesel BiodieselGreen Diesel

NOx Baseline +10 -10 to 0

Cetane 40-55 50-65 75-90

Cold Flow Properties Baseline Poor Excellent

Oxidative Stability Baseline Poor Excellent

Natural Oil/ Grease

+Hydrogen

Green DieselGreen Diesel + Propane

+ Glycerol Biodiesel (FAME)Biodiesel (FAME)

Natural Oil/ Grease

+ Methanol

Performance Comparison

Process Comparison vs. Biodiesel

Ecofining: Implementation Options

Feedstocks

Rapeseed

Tallow

Jatropha

Soybean

Algal Oils

Palm Oil

2. Revamp existing DHT

4. Stand-alone Hydroprocessing/Isomerization(Ecofining Unit)

1. Co-ProcessedHydroprocessing

3. Integrate with new or existing DHT

UOP 5149-12

UOP/ENI EcofiningTM Process to Produce Green DieselPreferred Bio Derived Diesel of ACEA

Green Diesel vs. Biodiesel (FAME)

Natural Oil/ Grease

+ Glycerol

Biodiesel (FAME) Green Diesel

+ Propane

HydrogenMethanol

Petroleum ULSD

Biodiesel (FAME) Green Diesel

Oxygen Content, % 0 11 0

Specific Gravity 0.84 0.88 0.78

Sulfur content, ppm <10 <1 <1

Heating Value MJ/kg 43 38 44

Cloud Point, °C -5 -5 to +15 -30 to -10

Cetane 40 50-65 70-90

Lubricity Baseline Good Baseline

Stability Baseline Poor Baseline

UOP 5149-13

-$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

NP

V,

$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

Breakeven Analysis: Sensitivity to Feed Oil Prices

Economics of Oil Upgrading

• Strongly dependent on price of starting oil

• Requires source of hydrogen to modify oil – expense

• Upgrading steps complimentary with traditional refinery operations

• Capital charge dependent on access to existing facilities

Second Generation Option

Lignocellulosic Biomass Processing Options

SolidBiomass

Direct Combustion

Fast Pyrolysis

PyrolysisOil

Gasification

SynGas

Heat & Power

TransportFuels

FischerTropsch

Upgrading

Hydro-cracking/Dewaxing

Fermentation/Catalysis

Bioethanol/Biobutanol

Envergent Route to Energy

UOP 5363-08

Pyrolysis Oil to Energy & Fuels Vision

Fast Pyrolysis

Electricity Production

Transport Fuels

(Gasoline, Jet, Diesel)

Fuel Oil Substitution

Availab

le for S

aleC

om

mercially

available in

2012

Phased Commercialization

Biomass

Ag ResidueAg Residue

Pyrolysis Oil

Forest FiberForest Fiber

Energy/Fuels

P P

P P

Rapid Thermal Processing (RTPTM) Technology

Pyrolysis Oil

Solid Biomass

Commercially Proven Patented TechnologyUOP 5363-10

RTP Operating History & Commercial Experience

• Commercialized in the 1980’s• 7 units designed and operated in the US & Canada• Continuous process with >90% availability

Significant Commercial Experience

PlantYearBuilt

Operating Capacity (Metric Tonnes Per

Day)Location

Manitowoc RTP – 1 1993 30 Manitowoc, WI, USA

Rhinelander RTP – 1 1995 35 Rhinelander, WI, USA

Rhinelander Chemical #2 1995 2 Rhinelander, WI, USA

Rhinelander RTP – 2 2001 45 Rhinelander, WI, USA

Rhinelander Chemical #3 2003 1 Rhinelander, WI, USA

Petroleum Demo # 1 2005 300 barrels per day Bakersfield, CA, USA

Renfrew RTP – 1 (Owned and

operated by Ensyn)2007 100

Renfrew, Ontario, Canada

Note: design basis for wood based plants assumes feedstocks with 6 wt% moisture content.

• FCC technology is key process in gasoline production

• UOP has been designing FCC units since the early 1940’s – one of the co-inventors

• Licensed over 250 units – more than 50% of world-wide capacity

• Unit sizes from 1,500 to 200,000 BPD capacity

UOP 5121-03

RTPTM UOP FCC

FCC Experience Enables Scale-up

UOP FCC Background

RTPTM Unit Process Diagram

Pyrolysis Oil

Ash & Sand

Flue Gas to Rotary Kiln Drier

Reactor

Fuels Burner

Hot Sand

Char & Sand

Atmospheric Air

Reheater

By product Gas

Reheater Flue Gas

Sized & Dried Biomass

Primary Condenser

Secondary Condenser

Fibre Bed Filter

Surge Bin

Feed Bin

FeedSystem

Conversion

Quench & Separation

Heat forMoisture

Reduction

Minimal Net Utilities – RTP Is Self sustaining Process With Reduced Carbon Footprint

UOP 5363-11

Feedstock Sources

Cellulosic Feedstocks Widely Available

Forestry and Pulp and Paper– Wood chips, sawdust, bark– Lignin

Agricultural– Residues - straw, expended fruit

bunches from palm (EFB), other– Purpose-grown energy crops –

miscanthus, elephant grass Post-consumer

– Construction and Demolition Waste, Categories 1 & 2

– Municipal solid waste (future) USDA study 2005 - > 1 billion

ton per year available in United States alone

0

50

100

150

200

250

300

350

Africa

Mid

dle &

South

Am

eric

aIn

dia

Oth

er A

sia

China

United

State

s

Former

Sovi

et U

nion

West

ern

Europe

Canad

a

Easte

rn E

urope

Austra

lia &

New

Zea

land

Mid

dle E

ast

Mex

ico

Japan

South K

orea

Te

ch

nic

al

Bio

ma

ss

Re

so

urs

e

Po

ten

tia

ls (

Mto

e)

Firewood

Waste

Energy Crops

Agricultural Residues

Bagasse

Forestry & Wood Processing Residues

Regional Technical Biomass Potentials in 2050(Mtoe/yr)

Source: VTT, 2007a

UOP 5363-12

Feed Handling / Preparation

• Water is a heat sink• Dried to 5-6 wt%

moisture content for efficient RTPTM reactor operation

• Size impacts heat transfer• Biomass sized to 0.125-

0.25 inch (3-6 mm)

• Capacity of unit expressed on bone dry feed basis• BDMTPD• Zero water content

RTP Storage

Raw BiomassUp to 40 wt%

Moisture

Prepared Biomass“As Fed”5 – 6wt% Moisture

0.125 to 0.25"Pyrolysis Oil

“As Produced”Feed Handling

RTP is Self-Sustaining – Excess Heat Dries Raw Biomass

RTPTM Product Yields

Cellulosic Feedstock Flexible with High Yields of Pyrolysis Oil

Feed, Wt%

Hardwood Whitewood 100

Typical Product Yields, Wt% Dry Feed

Pyrolysis Oil 72.9

By-Product Vapor 13.3

Char 13.8

Biomass Feedstock Type

Typical Pyrolysis Oil Yield, Wt% of Dry Feedstock

Hardwood 70 – 75

Softwood 70 – 80

Hardwood Bark 60 – 65

Softwood Bark 55 – 65

Corn Fiber 65 – 75

Bagasse 70 – 75

Waste Paper 60 – 80

400 TPD of Hardwood

Yields For Various Feeds

UOP 5363-13

RTPTM Pyrolysis Oil Properties

Suitable for Energy Applications

Fuel MJ / Litre BTU / US Gallon

Methanol 17.5 62,500

Pyrolysis Oil 19.9 71,500

Ethanol 23.5 84,000

Light Fuel Oil (#2) 38.9 139,400

Comparison of Heating Value of Pyrolysis Oil

and Typical Fuels

• Pourable, storable and transportable liquid fuel

• Energy densification relative to biomass• Contains approximately 50-55% energy

content of fossil fuel• Stainless steel piping, tankage and

equipment required due to acidity• Requires separate storage from fossil

fuels

Pyrolysis Oil: Alternate Revenue Stream

• Development of pyrolysis oil as a well-defined commodity critical to success• Producer and consumer

confidence• ASTM standard specification

for use of pyrolysis oil in industrial burners is a key first step

PROPERTY VALUE TEST METHOD

Gross Heat of Combustion, MJ/kg Point, oC

15 min ASTM D240

Pyrolysis Solids Content, wt%

2.5 max ASTM D7544, Annex I

Water Content, wt%

30 max ASTM E203

pH report ASTM E70

Kinematic Viscosity, cSt @ 40 °C

125 max ASTM D445

Density, kg/dm3 @ 20 °C

1.1 – 1.3 ASTM D4052

Sulfur Content, wt%

0.05 max ASTM 4294

Ash Content, wt%

0.25 max ASTM 482

Flash Point, oC 45 min ASTM D93, Procedure B

Pour Point, oC -9 max ASTM D97

ASTM D7544, Standard Specification for Pyrolysis Liquid Biofuel

Comparison of Cost of Selling PyOil vs. Making PyOil

0

0.2

0.4

0.6

0.8

1

Selling PyOil Making PyOil

$U

S/U

S G

allo

n

Pyrolysis Oil Energy Applications

Compatible with specialized turbines

Specialized burner tips improve flame/burning

Convert to steam to use existing infrastructure

Use as a blend in diesel engines

Upgradable to hydrocarbon fuels

Multiple Applications for Pyrolysis Oil, a Renewable Fuel Available Today

GasTurbine

DieselEngine

Heat

ElectricityCHP

GreenGasoline,

GreenDiesel &

Green Jet

Fischer-Tropsch

SyngasGasification

OptimizedUOP

UpgradingTechnology

FuelBurner

Hydro-cracking/Dewaxing

RTPUnit

UOP 5363-14

Pyrolysis Oil: Replacement of Fossil Fuels to Generate Heat

0

0.5

1

1.5

2

Buying # 2 Fuel Oil Making PyOil

$U

S/U

S G

allo

n

• Specialized burner tips improve flame/burning

• Low emissions (NOx, SOx)• Fuel consistency - ASTM

D7544• Flexibility to decouple

pyrolysis oil production from energy generation (location and time)

• GHG emission reduction of 70-90%

• Low cost liquid biofuel• ~40% cheaper to make and use

pyrolysis oil than to purchase #2 fuel oil on an equivalent energy basis

• 400 BDMTPD RTP Unit• Assumes 60 $US/bbl crude• Includes RTP operating cost and 15-yr straight

line depreciation of CAPEX• 330 Days per Year

Comparison of Cost of Buying #2 Fuel Oil vs. Making Pyrolysis Oil

~ 8 $US Million per Year Savings

RTPTM Economics – Fuel Oil Substitute

Comparison of Cost of RTP Operation to Purchasing Equivalent Amount of Fuel Oil

• 400 BDMTPD RTP, hardwood whitewood feed; 330 days per year• #2 Fuel Oil scaled from 28 Nov 08 WTI Spot, 55 $US/bbl, & 1.67 $US/USGal for #2 Fuel Oil, Source EIA• Pyrolysis oil contains 55% of energy content of fuel oil, by volume. • 15 year straight line depreciation included in cost of operation; $US 30 million RTP ISBL CAPEX

De

live

red

&D

ry F

ee

ds

toc

k C

os

t, $

US

/Me

tric T

on

ne

5.0

6.0

7.0

8.0

9.0

10.0

11.0

12.0

13.0

14.0

15.0

15 20 25 30 35 40 45

Crude Oil Price, $US/barrel

Mil

lio

n $

US

/ye

ar

40

30

50

Cost of B

uying Equivalent A

mount of #

2 Fuel Oil

40 $US/MT FeedstockBreaks even @ ~28 $US/barrel

Economic Solution for Fuel Oil Substitution

Pyrolysis Oil: Production of Green Electricity

• Compatible with specialized turbines

• Green electricity production cost is 0.12 $US/kW-h• Includes RTP operating cost and

15-yr straightline depreciation of CAPEX (including gas turbine)

• Experience in stationary diesel engine as blend with fossil fuel• Operation with 100% pyrolysis

oil under development

• Commercial application expected by 2Q2011

Pyrolysis Oil Upgrading

• Objectives• Remove oxygen molecules

• Reduce acidity and viscosity

• Break up molecules to make high octane gasoline or diesel/jet precursors

• Commercialization expected in 2012

• Solution• Thermochemical upgrading;

leverage existing hydroprocessing technologies

• Preliminary Results• 30 Wt% hydrocarbon yield

from dry biomass

Fuel & Property Preliminary Value

Gasoline Approximate Yield, % Boiling Range, °C Octane Number

54IBP - 193

89

Diesel Approximate Yield, % Boiling Range, °C Cetane Number

35193 – 325

31.5

Heavies Approximate Yield, % Boiling Range, °C

10 – 20325+

Achieved in Lab, Working on Stability and Scale

Preliminary Yields from Hydrocarbon

UOP 5363-18

Partial Deox

PY Oil Stabilizer

Light acids/ oxygenates may be used to supplement H2 generation

Integration at the commercial plant level:

A number of options exist for integration of py oil into refinery processes:

– As stabilized py oil

– As partially or fully deoxygenated py oil

– For by-products (light acids, oxygenates) as H2 generation

Integration into Commercial Refinery

UOP 5363-19

Integrated Biorefinery Demonstration

• UOP has received a DOE grant to demonstrate fuels technology from conversion of second generation feedstocks

• Demonstration to be done at a refinery location, with commercial partners

• Fuel sourced from pyrolysis technology is based on renewable feedstocks• Waste biomass

• On purpose energy crops

• C&D wastes

• Completely fungible fuels is the objective of the project

• Technology development that complements traditional refinery technology

Demonstration Plant to Start up by 2014UOP 5363-20

Pyrolysis Oil vs. Fossil Fuel LCA

0

10

20

30

40

50

60

70

80

90

Car

bo

n D

ioxi

de,

K g

CO

2/G

J

Heating Oil Natural Gas Pyrolysis Oil

Production Use

Canadian Scenario Sawmill ResiduesRTP unit located at sawmill siteFeed Transportation Distance = 0

PyOil 88% lower GHG than Petroleum-derived heating oil

LCA Result courtesy of Don O’Connor

(S&T)2 Consultants Inc.11657 Summit CrescentDelta, BCCanada, V4E 2Z2

Significant GHG Benefits With Biofuels

Carbon Dioxide Impact

UOP 5363-21

Pyrolysis Oil vs. Fossil Fuel LCA

Pyrolysis Oil Production foot printsimilar to fossil energy alternativesAssumed biomass transport distances

200 km for logging residues 25 km for short rotation forest crops

Pyrolysis Oil Life Cycle foot printGreener than other alternatives Carbon neutral combustion emission 70-88% lower GHG emissions SOx emissions similar to Natural Gas

Comparison of GHG EmissionsCradle to Delivered Energy

0

20

40

60

80

100

120

PetroleumCrude Oil

HardCoal

gC

O2

eq/M

J

NaturalGas

CanadianOil SandsCrude Oil

PyOilfrom

LoggingResidues

PyOilfrom

Willow

PyOilfrom

Poplar

Energy ExtractionGHG Emissions

Comparison of GHG EmissionsCradle to Delivered Energy, and Burned

0

20

40

60

80

100

120

PetroleumFuel Oil

HardCoal

gC

O2

eq/M

J

NaturalGas

PyOilfrom

LoggingResidues

PyOilfrom

Willow

PyOilfrom

Poplar

Life Cycle GHG Emissions

through combustion

RTPTM Project Benefits

Pyrolysis to Energy Now – Transport Fuels in 2012

Environment & Social Reduction of

greenhouse gases and emissions

Waste disposal

Minimum environmental Impact

Agriculture development

Employment

Technical Proven application Feedstock flexibility Minimal net utilities Storable product allows

decoupling from end user

Energy Security Energy diversification Reduction of fossil

energy requirements

Economics Economic solution

for renewable energy Competitive relative to

fossil fuels Leverages existing

assets Provides alternate

revenue stream

UOP 5363-22

Biofuels and RefiningA Compatible Future

• Several options exist to address the growing demand for renewable fuels• Choice of option depends strongly on available feed

• Economics tied to feed supply and alternate feed uses

• Triglyceride oil starting points give immediate transport fuels solution

• Cellulosic materials provide an energy substitute

• Longer term transport solution

• RTP technology for conversion of biomass to an energy delivery intermediate• Commercially proven technology: 8 units designed and operated

• Reliable operation with 90% on-line availability similar to refining operations

• Cost competitive with fossil fuel oil (depending on crude price and feedstock cost)

• 25-30% cheaper than #2 Fuel Oil on energy basis

• Transport fuels technology available soon• DOE demo in progress

• Alternate fuel with secure supply chain• Tangible environmental benefits

UOP 5363-23

UOP 5363-24