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Biomass Pyrolysis to Liquid Fuels in the U.S.
2G 2020 Biofuels Seminar
Helsinki, Finland
August 30, 2012
Douglas C. Elliott
Outline Department of Energy and its Solicitations Developments at PNNL Other Contributors
Distributed Pyrolysis and Centralized Bio-oil Processing
StabilizationPyrolysisBiomass
Mixed WoodsMixed Woods
Corn StoverCorn Stover
Deoxygenate
GasolineDieselJetChemicals
Holmgren, J. et al. NPRA national meeting, San Diego, February 2008.
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CTG Teams
FSL Algae BM-to-Sugar BM-to-Bio-Oil Sugar-Upgrading Bio-Oil Upgrading Communications Analysis and Sustainability
Steering Committee
John Ferrell Melissa Klembara Neil Rossmeisel
Kevin Craig
John Ferrell Liz Moore
Kevin Craig
Valerie Sarisky-Reed
Brian Duff Steve Thomas
Joyce Yang Kevin Craig
Valerie Sarisky-Reed
Brian Duff Steve Thomas
Liz Moore Kevin Craig
Valerie Sarisky-Reed
John Ferrell Brian Duff
Neil Rossmeisel Kevin Craig
Valerie Sarisky-Reed Brian Duff
Melissa Klembara Christy Sterner
Kevin Craig
Alison Goss Eng John Ferrell
Lead Steve Thomas Christy Sterner Neil Rossmeisel Melissa Klembara Joyce Yang Liz Moore
Howard Marks Barbara Twigg
Ranyee Chiang Alicia Lindauer-
Thompson Kristen Johnson
Sub-lead Travis Tempel Joyce Yang Leslie Pezzullo Kevin Craig Bryna Berendzen Paul Grabowski
Technology Expertise
Sam Tagore Roxanne Dempsey
Roxanne Dempsey Physical Scientist
+
Gene Petersen Leslie Pezzullo
ChemE -
Bryna Berendzen Leslie Pezzullo
ChemE +
Gene Peterson Bryna Berendzen
ChemE+
Capital Projects
Elliott Levine Travis Tempel
Travis Tempel Glenn Doyle Chad Schell
Paul Grabowski Elliott Levine
Glenn Doyle Christy Sterner
Paul Grabowski Chad Schell Kevin Craig
Feedstock / Conversion
Interface
Leslie Pezzullo Joyce Yang Sam Tagore Mark Decot Roxanne Dempsey
Physical Scientist -
Physical Scientist - Mark Decot Physical Scientist -
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Bio-Oil Production and Upgrading
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Upgrading Bio-Oil
Current Efforts • Pyrolysis oil stabilization awards (UOP, VA Tech, UMass, IowaStateU, RTI) • $25 million integrated biorefinery demo fast pyrolysis and hydroprocessing (UOP) • Integrated Hydropyrolysis and Hydroprocessing biorefinery projects (GTI) • Stabilized pyrolysis oil upgrading awards (GTI, Battelle, PNNL, W.R. Grace) • Roadmap for hydrocarbon biofuels from thermochemical routes to 2022
Barriers • Catalyst stability and performance for bio-oil processing
– Refinery catalysts are designed to perform without water, tars, acidity – High reactivity of bio-oils leads to coking
• Bio-oil quality and yields – Oxygen and water contents, acidity; low heating value
• Insertion of bio-oil into existing petroleum refinery infrastructure • Bio-oil component polymerization and char
Raw and Upgraded Bio-oil
Thermochemical Direct Liquefaction of Biomass Fast Pyrolysis 500°C, 1 atm, dry, finely divided, < 1 second Inert atmosphere Non-catalytic
Hydrothermal Liquefaction (pyrolysis in aqueous) ~350ºC, 200 atm, biomass slurry in water, minutes Reducing gas (sometimes) Catalyst (sometimes)
Alkali Metals
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NABC Downselect
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Six Initial Strategies Proposed By NABC
• Syngas-to-distillates has not been selected to continue • Catalytic fast pyrolysis will be pursued outside of NABC by commercial entities to in order to
accelerate time to market • Hydrothermal liquefaction and Hydropyrolysis selected for additional funding at lower
level • Fermentation of sugars and catalytic conversion of sugars selected for additional funding at
higher level
Hydrothermal Liquefaction and Hydrotreating Process Improvement as part of National Advanced Biofuels Consortium (NABC)
Bench-scale testing in continuous-flow system Increase bio-oil yield by increased slurry concentration and aqueous recycle Evaluate aqueous byproduct utilization
Recovery of dissolved organics Gasification of organics
Catalytic hydrotreating of product oil to produce hydrocarbon liquids TechnoEconomic Assessment and Life-Cycle Analysis as part of down-select at end of 1st year (August 2011)
Hydrothermal Liquefaction and Hydrotreating International collaborations supported by DOE/OBP
Canada Macroalgae resource assessment Kelp feedstocks compared from Atlantic and Pacific coasts HTL of Pacific seaweed (16% dry solids slurry)
25 wt% (DAF) oil yield; 44% carbon yield as oil 8.3% oxygen content in bio-oil (dry basis) 4.3% N and 0.3% S in bio-oil (dry basis)
Australia Bagasse and lignin-enriched Bagasse (hydrolyzed, sugar-extracted)
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OBJECTIVE: Target analysis and process development in thermochemical liquefaction to enable the
commoditization of bio-oils for hydrocarbon biofuel production with industrial (refinery) off take partners. Two topic areas will be supported:
1. Ideal for technology providers that have not yet formed bio-oil off take agreements. Necessitates in-depth TEA/LCA and formation of a refinery partner for continuation onto phase II.
2. Ideal for technology providers with a pre-existing refinery partner who are able to propose a complete pathway from feedstock through final hydrocarbon biofuel.
VALUE: BOSC Will:
• Benchmark state of technology for thermochemical liquefaction pathways to produce stable bio-oils for upgrading in existing petrochemical refineries.
• Defining market sizes and value chains for bio-oil commodities, as specified by refinery partners.
• Develop technologies and forge partnerships at varying technology readiness levels which can be leveraged in the OBP portfolio and in a complementary FOA slated for FY13.
TARGET AUDIENCE: Private industry, national laboratories and universities
Bio-Oil Stabilization and Commoditization (BOSC) FOA
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OBJECTIVE: Support outdoor phototrophic algae research and development projects in two topic areas:
1. Nutrient and water use in algal production systems 2. Preparation of algae testbed facilities
VALUE: ASAP Will:
• Support development of innovative technologies to capture and recycle water and nutrients. This will support reduced OPEX costs and improved sustainability profiles of large-scale operations.
• Develop testbed facilities that serve as engines for algal technology innovation, job training, and validation. This will accelerate capacity building for algal biofuels technology.
• Create knowledge of long-term cultivation data necessary to understand and promote algae biomass production. This will provide validated growth and productivity data to the design case and state-of-technology models and support setting MYPP performance targets.
TARGET AUDIENCE: Private industry, national laboratories and universities
Advancements in Sustainable Algae Production (ASAP) FOA
Hydrotreating Catalyst Bed Design
Challenge: Catalyst Lifetime
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Fast Pyrolysis Hydrotreatment
char Ligno-cellulosic biomass
gas
aqueous
FLUID
IZED
BE
D
RE
AC
TOR
Diesel Jet Fuel Gasoline
H2
Bio-oil
Gas
recy
cle
Ebu
llate
d B
ed
Liqu
id re
cycl
e
Gas recycle/ reforming
H2
HC
HT
Bio-oil
Research Activities: 2004-2006 Continuous-flow bench-scale reactor tests have been performed to test catalysts and processing conditions.
26 hydroprocessing tests 6-95 hour long
Recovered products were analyzed at PNNL to determine composition OBP Bio-oil Upgrading
Elliott, D.C.; Neuenschwander, G.G.; Hart, T.R.; et al. 2006. In: Science in Thermal and Chemical Biomass Conversion, pp. 1536-1546, CPL Press, Newbury Berks, UK. Elliott, D.C.; Hart, T.R.; Hu, J.; Neuenschwander, G.G. “Palladium Catalyzed Hydrogenation of Bio-Oils and Organic Compounds.” U.S. Patent #7,425,657, issued September 16, 2008. and U.S. Patent #7,956,224, issued June 7, 2011.
Research Activities: 2007-2009
Continuous-flow bench-scale reactor tests have been performed to test catalysts and processing conditions.
99 HT 49 HC
6-20 hour long Recovered products are analyzed at PNNL to determine composition and value UOP CRADA
Elliott, et al. Environmental Progress & Sustainable Energy 28(3), 441-449;
Research Activities: 2009-2012 Continuous-flow bench-scale reactor tests have been performed to test catalysts and processing conditions.
60 HT 1 shift to 1 week long
Recovered products are analyzed at PNNL to determine composition and value CORE, VTT, NABC, NAABB, BCO
Elliott, D.C.; Hart, T.R.; Neuenschwander, G.G.; Rotness, L.J.; Olarte, M.V.; Zacher, A.H.; Solantausta, Y. 2012. “Catalytic Hydroprocessing of Fast Pyrolysis Bio-oil from Pine Sawdust.” Energy & Fuel 26, 3891-3896
Ebullated-Bed Bio-oil Hydroprocessing
Recirculating concept avoids catalyst fouling New catalyst formulations required Bench-scale system installed in BSEL-158
Jet Fuel Produced from Pyrolysis Oil
Density, g/mL 0.8636 0.8630Degree API 32.18 32.29Flash point, °C 51.5 51.5Oxygen, mass % 0.13 < 0.02
Pyrolysis jet fuel was lightly treated to remove residual water and mixed with synthetic paraffinic kerosene (SPK) to produce a 100% biojet fuel.
PNNL product
Refined PNNL product
42.4 - 44.2 wt% jet fuel distillate by batch vacuum distillation
The Future: 100% Renewable Jet
The hydroplane ran on 98% Bio-SPK and 2% renewable aromatics Jet A1
Spec Starting
SPK Woody Pyrolysis Oil
Aromatics Freeze Point (oC) -47 -63 -53 Flash Point (oC) 39 42 52 Density (g/mL) 0.775 0.753 0.863
10 gal/d
200-400⁰C
135 atm
Bio-oil
30-350⁰C 1 atm
Hydrotreater Distillation
Catalytic Tubular Reactor
4.7 gal
Aqueous byproduct
Hydrocarbon product
Flammable Light distillate (naphtha, gasoline, jet)
Combustible Heavy distillate (diesel, cycle oil)
H2
2.5 l/h for 120 h (80 gal)
5 m3/hr (3 SCF/min 4320 SCF/d)
32 gal/wk
3.6 m3/hr Byproduct gas 90-95% H2 Balance light HC
17-21 gal
11-14 gal
KiOR Catalytic Pyrolysis Process
BIOMASS TRANSPORT TRANSPORTATION FUEL
TRANSPON FUEL
TRANSPORTATION FUEL
TRANSPION FUEL
Separator
Product Recovery
Cogenerator
Catalyst Regenerator
Rea
ctor
KiOR’s gasoline is the first renewable cellulosic gasoline that the EPA has registered for sale in the US
KiOR renewable gasoline will fuel cars this year—July 24, 2012 press release
Hydropyrolysis—Gas Technology Institute
Reformer
Gasoline/Diesel
hydrogen
Capable to produce fuel with a U.S. Department of Energy estimated selling price of less than $2.00/gallon in commercial production Technology licensed to CRI Catalyst Company headquartered in Houston, TX
Achieving commercial deployment in 2014
http://www.gastechnology.org/webroot/app/xn/xd577c.html?it=enweb&xd=6NewsRoom/2012/IH2_NR_04_17_2012.xml
100 lb/hr pilot plant
Other Participants NREL: Kristiina Iisa, Richard French, Stefan Czernik, Calvin Feik
Entrained flow PDU, small fluid bed, MBMS, semi-batch hydrotreater
ORNL: Jim Keiser, Shahab Sokhansanj, Jae-Soon Choi Corrosion studies, batch hydrotreating Torrefaction (BC) Upflow gasifier/Jenbacher engine
INL: Richard Boardman Feedstock supply, torrefaction
USDA-ERRC: Kwesi Boateng and Charles Mullan Small fluid bed, catalytic pyrolysis, pyroprobe
Other Participants
Mississippi State U: Prof. Phil Steel (DOE funded) Small auger, hydroprocessing, aqueous separation and utilization, bio-oil combustion
U Maine: Profs Clay Wheeler, Brian Frederick, Bill DeSisto (DOE funded/state funded)
Small fluid bed, chemical recovery, catalyst development Michigan State U: Prof Chris Saffron (USDA funded)
Small auger, pyroprobe Utah State U: Prof Foster Agblevor (state funded)
Catalytic pyrolysis U Mass-Amherst: Prof George Huber, Paul Dauenhauer
Pyrolysis chemical & physical mechanisms and modeling
Comparison of Routes
Pressure, atm
Temperature, ⁰C
LiquidHC/biomass, wt % yield
Fast Pyrolysis/Fixed-Bed 1/140 500/250-400 20-25
Fast Pyrol/Ebullated-Bed/HT 1/140/140 500/350/350 33?
HydroThermal Liquefaction/HT 200/102 350/400 26-37
Catalytic Pyrolysis/HT 1/140 500/250-400 19-?
Hydropyrolysis/HT 22/22 500?/400? 26
Conclusions
Fast Pyrolysis has a new higher profile in the DOE PNNL has a strong, ongoing effort in liquid fuels from biomass via pyrolysis There are many other participants in the field in the US The technology for catalytic hydroprocessing of bio-oil is moving into scale-up Next generation pyrolysis routes are getting strong support
Thank You! Acknowledgement:
Hydrotreating Iva Tews Gary Neuenschwander Mariefel Olarte Theresa Lemon Huamin Wang John Frye Michel Gray Heather Brown
Pyrolysis Miki Santosa Alan Zacher LJ Rotness Todd Hart John Lee Suh-Jane Lee