GTI Biorenewables

Vision, Challenges, Programs,

and Status

Terry Marker, Vann Bush, Eddie Johnston, Bill Liss, Jack Lewnard
Chicago Chapter AIChE September 15, 2009

August 2009
 Biofuels – Turning Up The Heat

>Introduction to GTI
>Biogas
>Biomass pre-treatment
>Thermochemical conversion options
─ Hydropyrolysis
─ Gasification
> Gas clean-up
> Syngas, fuel, and/or power
>tcBiomass Conference

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 What We Do

>GTI solves important energy challenges, turning

raw technology into practical solutions that
create exceptional value for our customers in the
global marketplace.

Energy Solutions… Delivered

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 Our Company at a Glance…

> Not-for-profit research,

with 65+ year history
> Facilities
─ 18 acre campus near Chicago
─ 200,000 ft2,
28 specialized labs
> $60 million in revenue
> Staff of 250 Flex-Fuel
Test
> A growing business Offices
& Labs
Facility

> 1000 patents; 500 products

> Commercial partners take our
technologies to market
Energy & Environmental Technology Center
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 Reducing carbon emissions to the environment

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 Renewable Energy - Premises

> Fastest growing area in energy R&D

─ Global R&D spending up 20% in 2006
─ Corporate $9.1B; Gov’t $7.2B

> Increased domestic (and continuing

international) concerns about energy
independence, sustainability, global
warming, and need to hedge fossil prices
Biofuels required to meet mandated RPS, renewable fuel targets in
many states and countries, with increasing interest from suppliers
and users for “green” natural gas

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Biogas- Nature’s Oldest Renewable
> Manure or waste to methane via anaerobic
digestion ideal for low-solids streams

> First recorded us in Assyria ca 10 BC to heat

bath water

> Millions of small systems in China and India

> US and Europe primarily using biogas for power

generation; missed opportunity for higher-value
uses

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Biogas – Composition and Potential
> Biogas basics
Human Related U.S. Methane Emissions
─ Produced from anaerobic digestion of (in TgCO2 equivalent)
biomass, typically dilute organic
waste stream Other Landfills
─ Digesters for manure, mixed ag
waste, wastewater treatment, and Wastewater
Treatment Natural Gas
landfills Systems

─ Composition 30-60% methane; Manure

Management
water-saturated with CO2 as primary Enteric
Fermentation
contaminant Coal Mining

─ Other contaminants specific to feed

Source: US Emissions Inventory 2005

> 1-2 TCF biogas total US recoverable

resource
> EU comparable or higher, but
market further developed

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 GTI Biogas Projects

> Altamont Landfill to LNG for Garbage Truck Fleet

─ Livermore CA, Waste Management and Linde

> Gills Onion to Fuel Cell

─ Digester Gas, FuelCell Energy Fuel Cells

> Landfill Gas to Hydrogen

> Pipeline Quality Renewable Gas from Dairy Waste Conversion

─ Utilities Participating (PG&E)
─ Guidance Paper on Gas Quality Issues

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Biogas Challenges
> Push
─ EU mandates to redirect organic waste from landfill, ban sludge and manure spreading, and
required access to gas and electric grid for renewable energy
─ US mandated biogas recovery from landfills and wastewater treatment plants
─ US emerging regulations on manure

> Pull
─ Renewable Portfolio Standards and favorable incentives (currently only when used for electricity)
─ Project developers and gas industry interested in pipeline quality gas
> Gas contract higher value than power contract, albeit with higher capital cost
> Creates transportable low-carbon fuel so electric utilities can reposition “fossil” NGCC
power plants as green facilities, meet RPS requirements, and access renewable credits
> CO2 credits from GHG abatement add 10% to product value

> Addressing the higher-value pipeline gas market requires a new

approach to gas processing and harmonized gas quality specifications
> Selling gas into the gas grid requires robust, fully-qualified, packaged
solution encompassing compression, clean-up, and instrumented custody
transfer

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 Biomass Pretreatment Project
Develop a process to render any ligno-cellulosic biomass into
material amenable to efficient gasification or pyrolysis.
 We must use forestry and agricultural
biomass sources to reach biofuel goals.
 Logistics of biomass supply is a major
economic and carbon intensity hurdle.
 Higher energy density bio-feedstock would
allow larger, more economic process scale.
 Gasification and pyrolysis both benefit from
feedstock consistency.

Gasification • Fuel gas

• Power
Versatile Pretreatment • Liquid fuels
Technology Pyrolysis • Chemicals

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 Treatment of Pine Chips
Before After
C, % 51.4 68.3
H, % 5.9 5.1
O, % 42.1 25.9
Ash, % 0.39 0.27
HHV (dry), 8,500 11,800
Btu/lb

• Treated material is friable and easily pulverized.

• Preliminary energy balance shows 86% recovery

of energy as treated solids.

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 Chemistry Issues for Biomass
Pyrolysis

• High temperature uncontrolled thermal reaction, makes free radicals,

causes condensation reactions making condensed ring polynuclear
aromatics and olefins and polymerization – retrograde reactions make
compounds harder to upgrade with hydroconversion

• No significant reduction in oxygen in pyrolysis step, pyrolysis oil and wood

have the same % oxygen and same heating content on BTU/lb basis

• Structure needs hydrogen to reduce olefins, avoid condensation reactions

and avoid retrograde reaction

• Biomass does not have polynuclear aromatics to start with but we create
them in pyrolysis step

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 Typical Structure of Lignin

Carbon= 64%
Hydrogen =6% Perfect structure for conversion to
Oxygen= 30% gasoline and aromatics

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 Integrated Hydropyrolysis and
Hydroconversion (IH2 )
CONVERSION OF BIOMASS DIRECTLY INTO GASOLINE AND DIESEL
• Fast biomass heat up maximizes liquid yield
• Hydroconversion with catalysts produces low-oxygen, low-acidity liquids
• Polynuclear aromatic components are not formed
• Self-sufficient process requires no supplemental water or hydrogen
• High-quality renewable gasoline and diesel products are produced

100

Over 90% lower 90

greenhouse gases in 80

70
renewable gasoline Fuel Combustion
g CO2 eq. / MJ

60
Fuel Transportation
from IH2 process 50 Fuel Production
Transportation of Feedstocks
compared to 40
Feedstock Production, RMA
30
petroleum-based 20
Feedstock Chemicals

fuels 10

0
Petroleum Diesel GTI RG Petroleum Gasoline

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 Product Property Comparison
Fast Pyrolysis Oil IH2 product
% Oxygen 50 <1.0% IH2 Advantages
% Water 20 <0.1% • Infrastructure-
TAN 200 <2 compatible products
Stability Poor Good
• Avoids “bad stuff”
Heating Value Btu/lb 6560 18000 made in pyrolysis –
% C4- 430° F Non-distillable 92 PNA, free radicals
% 430 - 650° F Non-distillable 8
• Higher energy density
% 650° F + Non-distillable <1 products
Compatibility with crude No Excellent
oil or refinery products
Relative transportation 1.0 0.3
cost

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 Gasification: High Temperature Option

SNG

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 GTI-Carbona Fluidized-Bed
Biomass Gasifier
 High carbon conversion, 95-98%+
 Capability to gasify a wide variety of
fuels, including coal/biomass mixtures
 Simple design with safe, reliable
operation
• Air-blown, enriched-air or oxygen-blown
operation
• Atmospheric to 30+ bara
 Operates at a lower temperature than a
OXYGEN or slagging gasifier (to 1000 C)
• Longer metal component and refractory
life
 Good turndown capability, 30 – 50%
 Demonstrated at commercial scale by
Carbona

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 GTI/Carbona Biomass Feedstocks

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 Scale-up History of
GTI Gasification Technology
1000
HP Biomass

LP Coal
2x300
HP Coal
8x150
Capacity, Tons/day

100
165
80 100
4040

24
30 20
10

10
8

1
RENUGAS Finland Shanghai Flex-Fuel Denmark
UGAS Pilot and PDU - Chicago Maui
Chicago China
1970 1975 1980 1985 1990 1995 2000 2005 2010

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 Flex-Fuel Test Facility:
Pilot-Scale Fluidized Bed Gasifier
• Pilot-scale process R&D
• Periodic test campaigns
• ~30 testing staff

• Biomass – 20 tpd w/air; 40 tpd w/oxygen

• Gasification Pressure to 27 bara
• Extensive On-line Syngas Analysis Systems

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 Biomass Gasifier Projects

1992 1994
100 ton per day Bioenergy Demo Plant
80 ton per day Gasification Pilot Plant in
in Maui, Hawaii using bagasse
Tampere, Finland using biomass & coal

2006 2003
165 ton per day CHP Plant in 40 ton per day Flex-Fuel Test Facility
Skive, Denmark using wood in Des Plaines, IL for biomass & coal
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 Synthesis Gas Process

Particle,
Hydrolysis,
Power
Alkali
Acid Gas
Removal
Removal CHP

Methanol
Fuel
Gasification
Trace Synthesis, DME
Treatment Removal Upgrading
Alcohols
FT Diesel
Hydrocarbon
Shift Gasoline
Reforming
Hydrogen
Separation
H2
SNG

GTI R&D GTI U-GAS®, Morphysorb®,

RENUGAS®, Ultra-Clean UCSRP,
Coal Biomass GPE bluegas, CrystaSulf® (+DO) UCSRP,
Biomass pretreatment, PWR Compact GTI Catalysts, Ultra-Clean CrystaSulf-DO®
Coal and Biomass pyrolysis Gasifier Tar Reforming Membranes Ultra-Clean Catalyst

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 Engineering New Catalysts For In-Process Elimination Of Tars
Alfred Universityfounded 1836

Value: Create lower-cost, high-performing catalysts for tar

reduction in biomass gasifiers

Scope: Engineer new catalyst forms, use GTI submerged combustion melter to economically
produce optimized catalysts for the reduction or elimination of tars in biomass gasification,
evaluate catalysts for in-bed tar reduction in Flex-Fuel Test Facility (FFTF)
Status: Created new technologies for producing catalysts. Successfully demonstrated catalyst
performance in lab trials with steam reforming of methane and with naphthalene as a
surrogate biomass tar. Conducted baseline tests in FFTF. Proceeding to second phase for
manufacture and testing of catalyst formulations.

NAPHTHALENE DECOMPOSITION STEAM REFORMING OF METHANE (800°C)

Ni Metal 100
100
95
Naphthalene Reduction, %

Methane Conversion (%)

90
90
Olivine
80
85

70
80
Reactor Temperature
900°C
850°C 60
75
800°C
750°C
70 50
Ni-olivine Catalyst 0 20 40 60 80 100
0 5 10 15 20 25 30 35 40 45 50
Elapsed Time, h Elapsed Time, h
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 Hydrogen Production from Biomass
> Laboratory Screening of H2 Membranes
─ Ceramic membranes
─ Metallic membranes
> Field Prototype Tests
─ Biomass gasifier
─ Integrated system
> guard-shift-membrane
SCHOTT ─ H2 flux, purity targets

•feed

•hydrogen
•membrane •Porous support
•Copper seal coated by carbon

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 2nd Generation Biofuel Production from Wood
by Fluidized Bed Gasification and F-T

Pilot Testing Program at GTI

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 Skive, Denmark
Combined Heat & Power Project
GAS FILTER
TAR
REFORMER TO STACK
GASIFIER

GAS BOILER
BIOMASS
COOLER

FLY ASH

DISTRICT HEATING
12 MWth
GAS SCRUBBING GAS BUFFER
TANK

POWER
WATER 6 MWe

GAS ENGINES
ASH
AIR & STEAM

Gasification plant Heat accumulator

Fuel storage
Fuel receiving and storage

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tcbiomass International Conference

> AIChE Special Rate:

─ $450 one day pass
─ $900 three day conference registration
─ Brochures/information at registration desk

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 Summary

 Many renewable bio-energy options; producing fungible products

that integrate with existing energy infrastructure is key
 Anaerobic digestion of low-solids wastes is energetically
favorable; biogas applications active area of RD&D
 Biomass pre-conditioning likely required for large-scale
aggregation for renewable fuels
 Gasification of high-solids biomass is energetically favorable
route to syngas, fuels, and CHP
 GTI is developing integrated hydropyrolysis route to address low-
temperature liquid fuels production
 tcbiomass is a great opportunity to learn more

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