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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

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Page 1: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

Biomass Pyrolysis to Liquid Fuels in the U.S.

2G 2020 Biofuels Seminar

Helsinki, Finland

August 30, 2012

Douglas C. Elliott

Page 2: Biomass Pyrolysis to Liquid Fuels in the U.S. · 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

Page 3: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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.

Page 4: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

4 | Biomass Program eere.energy.gov

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 -

Page 5: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

5 | Biomass Program eere.energy.gov

Bio-Oil Production and Upgrading

Page 6: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

6 | Biomass Program eere.energy.gov

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

Page 7: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 8: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

8 | Biomass Program eere.energy.gov

NABC Downselect

8

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

Page 9: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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)

Page 10: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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)

Page 11: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

11 | Biomass Program eere.energy.gov

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

Page 12: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

12 | Biomass Program eere.energy.gov

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

Page 13: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

Hydrotreating Catalyst Bed Design

Challenge: Catalyst Lifetime

13

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

Page 14: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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.

Page 15: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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;

Page 16: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 17: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

Ebullated-Bed Bio-oil Hydroprocessing

Recirculating concept avoids catalyst fouling New catalyst formulations required Bench-scale system installed in BSEL-158

Page 18: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 19: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 20: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 21: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 22: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 23: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 24: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 25: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 26: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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

Page 27: Biomass Pyrolysis to Liquid Fuels in the U.S. · Biomass Pyrolysis to Liquid Fuels in the U.S. 2G 2020 Biofuels Seminar Helsinki, Finland . August 30, 2012 . Douglas C. Elliott

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