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Progress and Outlook for Low Cost Pretreatment of Cellulosic Biomass for Biological Production of Fuels and Chemicals
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Progress and Outlook for Low Cost Pretreatment of Cellulosic Biomass for Biological Production of Fuels and Chemicals

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Presentation of Bin Yang for the Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane. …

Presentation of Bin Yang for the Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane.

Apresentação de Bin Yang realizada no "Workshop on Hydrolysis Route for Cellulosic Ethanol from Sugarcane"

Date / Data : February 10 - 11th 2009/
10 e 11 de fevereiro de 2009
Place / Local: Unicamp, Campinas, Brazil
Event Website / Website do evento: http://www.bioetanol.org.br/workshop1

Published in: Technology
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  • 1. Progress and Outlook for Low Cost Pretreatment of Cellulosic Biomass forBiological Production of Fuels and Chemicals Bin Yang and Charles E. Wyman Chemical and Environmental Engineering and Center for Environmental Research and Technology (CE-CERT) University of California Workshop on Hydrolysis Route for Cellulosic Ethanol From Sugarcane February 11, 2009 Campinas, Brazil
  • 2. Sustainable Alternatives for TransportationSustainable Primary Secondary HumanResources Intermediates Intermediates Needs Sunlight Wind Biomass Organic Fuels Ocean/ hydro TransportationGeothermal Hydrogen Electricity Nuclear Batteries By Lee Lynd, Dartmouth 2
  • 3. Reaction Pathways for Biomass Conversion High Temperature Cellulosic Conversion: Catalytic Pyrolysis, Conversion Liquefaction, in Supercritical, Gas Phase Oil Refining Gasification Reactions:Cellulosic Catalytic BiofuelsBiomass Cracking, Biochemicals Hydrotreating Catalytic Conversion in Low Temperature Aqueous Phase Cellulosic Conversion: Acid Hydrolysis Enzymatic Hydrolysis From George Huber, UMass 3
  • 4. Alternative Fuel Mandates in US From Energy Independence and Security Act of 2007 4
  • 5. Biological Processing of Cellulosic Biomass Biological processing of cellulosic biomass to ethanol and other products offers the high yields vital to economic success Biological processing can take advantage of the continuing advances in biotechnology to dramatically improve technology and reduce costs 5
  • 6. Historical and Projected Cellulosic Ethanol 700 Costs Minimum Ethanol Selling Price (cents/gal) 600 Cost reductions 500 to date 400 Future goal 300 200 100 0 2009 2007 2008 2006 2010 2005 2004 2003 2012 2002 2001 2011 Enzyme Feedstock ConversionNREL Modeled Cost 6
  • 7. Key Processing Cost Elements ~9% of cost Total ~39% of cost Cellulase enzyme ~18% of cost~33% of cost Biomass Stage 2 Residual solids: Stage 1 Enzymatic cellulose, Pretreatment Solids: cellulose,Chemicals hydrolysis hemicellulose, hemicellulose, lignin lignin ~12% of cost Dissolved sugars, oligomers Dissolved sugars, oligomers, lignin Stage 3 Sugar fermentation 7
  • 8. Pretreatment Reduce biomass recalcitrance to attack by enzymes High sugar yields are vital 8
  • 9. Disruption of Cellulosic Biomass by Pretreatment Heat Cellulose Lignin Disruption Hemicellulose
  • 10. Importance of Pretreatment Although significant, feedstock costs are low relative to petroleum In addition, feedstock costs are a very low fraction of final costs compared to other commodity products Pretreatment is the most costly process step:  Low yields without pretreatment drive up all other costs more than amount saved  Conversely enhancing yields via improved pretreatment would reduce all other unit costs Need to reduce pretreatment costs to be competitive 10
  • 11. Central Role and Pervasive Impact of Pretreatment for Biological Processing Enzyme production Harvesting, Biomass Enzymatic Sugar storage, Pretreatmentproduction hydrolysis fermentation size reduction Hydrolyzate Hydrolyzate Ethanol conditioning fermentation recovery Residue Waste utilization treatment 11
  • 12. Feedstocks Vs. Yields Biomass Glucan Xylan Theoretical Potential feedstock % % Ethanol Yield Real Ethanol (gal/ton) Yield (gal/ton)Corn stover 36.1 21.4 105 89Switchgrass 35.0 21.8 104 88Sugarcane bagasse 38.6 20.4 108 92 Poplar 43.8 14.9 107 91Aspen wood 44.8 14.9 109 98Miscanthus 46.0 19.8 120 102
  • 13. Economic Impact of R&D-Driven Improvements Increase hydrolysis yield 3% Overcoming the 13% recalcitrance of Halve cellulase loading biomass Eliminate pretreatment 22% Consolidated bioprocessing 41% (CBP) Simultaneous C5 & C6 Use 6% Improving Increased fermentation 2% production of yield targeted Increased ethanol titer 11% products Increased ethanol titer following 6% CBP 0% 10% 20% 30% 40% 50% Error bars denote two Processing Cost Reduction different base cases From Nature Biotech. 200813
  • 14. Key Features of CAFI Leading Pretreatments for Corn Stover Pretreatment Temperature, Reaction Chemical Percent Other notesAcid system oC time, agent used chemical minutes used Dilute acid 160 20 Sulfuric 0.49 25% solids concentration during run in batch tubes acid Flowthrough 200 24 none 0 Continuously flow just hot water at 10mL/min for 24minutes Partial flow 200 24 none 0 Flow hot water at 10mL/min from 4-8 minutes, batch otherwise pretreatment Controlled 190 15 none 0 16% corn residue slurry in water pH AFEX 90 5 Anhydrous 100 62.5% solids in reactor (60% moisture dry weight basis), 5 ammonia minutes at temperature ARP 170 10 ammonia 15 Flow aqueous ammonia at 5 mL/min without presoaking Lime 55 4 weeks lime 0.08 g Purged with air.Base CaO/g biomass 14
  • 15. CAFI Feedstock: Corn StoverFrom BioMass AgriProducts, Harlan IA and Kramer Farm, Wray, CO Component Composition Ethanol yield wt % gal/ton Glucan 36.1 62.1 Xylan 21.4 37.7 Arabinan 3.5 6.2 Mannan 1.8 3.1 Galactan 2.5 4.3 Lignin 29.1 Protein nd Acetyl 3.6 Ash 1.1 Uronic Acids nd Extractives 3.6 Total maximum ethanol potential 113.3
  • 16. Overall Yields for Corn Stover at 15 FPU/g Glucan Xylose yields* Glucose yields* Total sugars* Pretreatment Total Stage Total Combined system Stage 1 Stage 2 Stage 2 Stage 1 Stage 2 xylose 1 glucose total Maximum 37.7 37.7 37.7 62.3 62.3 62.3 100.0 100.0 100.0 possibleIncreasing pH Dilute acid 32.1/31.2 3.2 35.3/34.4 3.9 53.2 57.1 36.0/35.1 56.4 92.4/91.5 SO2 Steam 14.7/1.0 20.0 34.7/21.0 2.5/0.8 56.7 59.2/57.5 17.2/1.8 76.7 93.9/78.5 explosion Flowthrough 36.3/1.7 0.6/0.5 36.9/2.2 4.5/4.4 55.2 59.7/59.6 40.8/6.1 55.8/55.7 96.6/61.8 Controlled 21.8/0.9 9.0 30.8/9.9 3.5/0.2 52.9 56.4/53.1 25.3/1.1 61.9 87.2/63.0 pH AFEX 34.6/29.3 34.6/29.3 59.8 59.8 94.4/89.1 94.4/89.1 ARP 17.8/0 15.5 33.3/15.5 56.1 56.1 17.8/0 71.6 89.4/71.6 Lime 9.2/0.3 19.6 28.8/19.9 1.0/0.3 57.0 58.0/57.3 10.2/0.6 76.6 86.8/77.2 *Cumulative soluble sugars as total/monomers. Single number = just monomers. 16
  • 17. CAFI Feedstock: PoplarFeedstock: USDA-supplied hybrid poplar (Alexandria, MN)  Debarked, chipped, and milled to pass ¼ inch round screen Component Composition Ethanol yield wt % gal/ton Glucan 43.8 75.4 Xylan 14.9 26.1 Arabinan 0.6 1.1 Mannan 3.9 6.8 Galactan 1.0 1.8 Lignin 29.1 Protein nd Acetyl 3.6 Ash 1.1 Uronic Acids nd Extractives 3.6 Total maximum ethanol potential 111.1
  • 18. Sugar Yields for CAFI Standard Poplar at 15 FPU/g Glucan Xylose yields Glucose yields Total sugar monomers Pretreatment Total Total Combined system Stage 1 Stage 2 Stage 1 Stage 2 Stage 1 Stage 2 xylose glucose total Maximum 25.7 25.7 25.7 74.3 74.3 74.3 100 100 100 possible SO2 Steam Increasing pH 19.2/14.0 2.4 21.6/16.4 2.3 72.0 74.3 21.6/16.3 74.4 95.9/90.7 explosion Dilute acid 16.1 2.4 18.5 17.7 46.6 64.3 33.8 49.0 82.8 (Sunds) Controlled 21.2/1.0 8.8 30.0/9.8 1.4/0.1 42.3 43.7/42.4 22.6/1.1 51.1 73.7/52.2 pH AFEX 0.0 13.4 13.4 0.0 39.4 39.4 0.0 52.8 52.8 AFEX with 76.9/55. cellulase + 0.0 17.5/13.0 17.5/13.0 0.0 76.9/55.0 0.0 94.3/68.0 94.3/68.0 0 xylanase ARP 9.6/0.0 8.2/8.0 17.7/8.0 0.4/0.0 36.3 36.6/36.3 10.0/0.0 44.5/44.3 54.5/44.3 74.4/72. Lime 1.1/0.0 20.1/17.1 21.2/17.1 0.2/0.0 74.6/72.5 1.3/0.0 94.5/89.6 95.8/89.6 5*Cumulative soluble sugars as total/monomers. Single number = just monomers. 18
  • 19. Projected Costs Virtually the Same with Oligomer 1.75 Utilization (Black Bars) for Corn Stover 1.50MESP, $/gal EtOH 1.25 1.00 Dilute Acid Hot Water AFEX ARP Lime w/o Oligomer Credit w/ Oligomer Credit
  • 20. Opportunities to Reduce Pretreatment Cost Need to reduce cost from the operation units:  Energy use  Costs of chemicals  Containment costs  Size reduction requirements  Prefermentation conditioning Achieve high yields for multiple crops, sites, ages, harvest times While increasing yields And limiting inhibitors to bioprocessing Advanced pretreatment processes will pay big dividends Key: understand pretreatment mechanisms and how to improve yields 20
  • 21. Effect of Flow Rate on Xylan Removal from Corn Stover and Oat Spelt Xylan 100 Xylan/2mL/min 90 Xylan/25mL/min Percent of potential total xylose, % 80 Xylan/0mL/min 70 Corn stover/25mL/min 60 50 Corn stover/2mL/min 40 30 Corn stover/0mL/min 20 10 0 0 2 4 6 8 10 12 Time, minutes 21
  • 22. Yield of Xylan Oligomers and Total Xylan Recovery in Hydrolysate Flow rate Yield, % Feedstock mL/min Total DP1 to Long Ratio of xylan 30 chain shorter chain recovery1 oligomer2 to longer chain oligomer Corn stover 0 (Batch) 38.1 28.1 10.0 2.8 2 48.2 20.3 27.9 0.7 25 73.3 9.1 64.2 0.1 Oat spelt xylan 0 (Batch) 73.1 30.1 43.0 0.7 2 92.1 0.3 91.8 0.003 25 91.1 0.4 90.8 0.0041. Total xylan recovery = yield of xylose in hydrolysate+ yield of oligomers in hydrolysate (xylose equivalent);2. Yield of long chain oligomer (DP>30) = total xylan recovery – yield of DP1∼30. 22
  • 23. Effect of Xylan Removal on Digestibility of Corn Stover for Batch and Flowthrough Reactors 100 90 80 Enzymatic digestibility,% 70 60 50 40 30 Uncatalyzed batch tube (160-220C, 5% solid loading) Catalyzed batch tube (160-220C, 5% solid loading, 0.1% acid) Uncatalyzed flowthrough (160-220C, flow rate of 2ml/min) 20 Uncatalyzed flowthrough (160-220C, flow rate of 7.5ml/min) Uncatalyzed flowthrough (160-220C, flow rate of 25ml/min) Catalyzed flowthrough (160-220C, flow rate of 2ml/min) Catalyzed flowthrough (160-220C, flow rate of 7.5ml/min) Catalyzed flowthrough (160-220C, flow rate of 25ml/min) 10 0 20 40 60 80 100 Xylan removal,% 23
  • 24. Effect of Lignin Removal on Digestibility of Corn Stover for Batch and Flowthrough Reactors 100 90 80 Enzymatic digestibility,% 70 60 50 40 30 Uncatalyzed batch tube (160-220C, 5% solid loading) Catalyzed batch tube (160-220C, 5% solid loading, 0.1% acid) Uncatalyzed flowthrough (160-220C, flow rate of 2ml/min) Uncatalyzed flowthrough (160-220C, flow rate of 7.5ml/min) 20 Uncatalyzed flowthrough (160-220C, flow rate of 25ml/min) Catalyzed flowthrough (160-220C, flow rate of 2ml/min) Catalyzed flowthrough (160-220C, flow rate of 7.5ml/min) Catalyzed flowthrough (160-220C, flow rate of 25ml/min) 10 0 10 20 30 40 50 60 70 80 90 Lignin removal,% 24
  • 25. Role of Lignin in Pretreatment Historically divergent opinions on role of lignin versus hemicellulose in access of enzymes to cellulose in pretreated biomass Our results suggest that lignin must be disrupted to achieve high enzymatic hydrolysis  Hemicellulose removal serves as a marker of lignin disruption but is not the cause of better digestion  Even better results if remove lignin  Lignin-xylan oligomers and their solubility could have a large effect on the rates and yields of lignocellulosic biomass pretreatment 25
  • 26. Mission of UCR Ethanol Research Improve the understanding of biomass fractionation, pretreatment, and cellulose hydrolysis to support applications and advances in biomass conversion technologies for production of low cost commodity products Develop advanced technologies that will dramatically reduce the cost of production 26
  • 27. Current Research Topics Diesel fuel from biomass – DARPA Effect of different pretreatments on enzymatic hydrolysis of poplar wood and switchgrass – US DOE  Lead Consortium with Auburn, Michigan State, NREL, Purdue, Texas A&M, U. British Columbia, and Genencor Pretreatment of cellulosic biomass for BioEnergy Science Center (BESC), $25million/yr DOE Center Continuous hydrolysis and fermentation – USDA Continuous fermentations of pretreated biomass - NIST Fundamentals of biomass pretreatment – Mascoma Corporation Evaluation of advanced plants – Mendel Biotechnology Enzyme inhibition by oligomers – Bourns College of Engineering 27
  • 28. 4 ” Example Experimental Systems Pretreatment tubes Pretreatment reactor Flowthrough ReactorPretreatment steam gun HTP pretreatment system Continuous Fermentation 28
  • 29. Biomass Refining Consortium for Applied Fundamentals and Innovation (CAFI) 29
  • 30. Agricultural and Industrial Advisory Board CAFI DOE ProjectQuang Nguyen, Abengoa Bioenergy Kendall Pye, LignolJim Doncheck, Arkion Life Sciences Wei Huang, LS9Gary Welch, Aventinerei Jim Flatt, MascomaMohammed Moniruzzaman, BioEnergy Intl Farzaneh Teymouri, MBIParis Tsobanakis, Cargill James Zhang, MendelJames Hettenhaus, CEA Richard Glass, NCGASteve Thomas, CERES James Jia, NorFalco SalesLyman Young, ChevronTexaco Joel Cherry, NovozymesMike Knauf, Codexis Mark Stowers, PoetJulie Friend, DuPont Ron Reinsfelder, ShellJack Huttner, Genencor Paul Roessler, Synthetic GenomicsDon Johnson, GPC (Retired) Carmela Bailey, USDAJeff Gross, Hercules Don Riemenschneider, USDAPeter Finamore, John Deere Kevin Gray, VereniumGlen Austin, Lallemand Ethanol Technology Chundakkadu Krishna, Weyerhaeuser 30
  • 31. The BESC Team: Recently Funded by DOE for $125 Million Over 5 YearsJoint Institute for Biological Sciences • Oak Ridge National Laboratory • University of Georgia • University of Tennessee • National Renewable Energy Laboratory • Georgia TechAlternative Fuels User Facility • Samuel Roberts Noble Foundation • Dartmouth • ArborGeni • Mascoma • Verenium • U California-RiversideComplex Carbohydrate Research Center • Cornell, Washington State, U Minnesota, NCSU, Brookhaven National Laboratory, Virginia Tech 31
  • 32. BESC - A Highly Integrated Cutting- Edge Research Team 32
  • 33. Closing Thoughts Biology provides a powerful platform for low cost fuels and chemicals from biomass  Can benefit both crop production and conversion systems The resistance of one biological system (cellulosic biomass) to the other (biological conversion) requires a pretreatment interface Advanced pretreatment systems are critical to enhancing yields and lowering costs Not all pretreatments are equally effective on all feedstocks Focus on 2 biologies - plants and biological conversion - without integrating their interface – pretreatment – will not significantly lower costs 33
  • 34. Charles Wyman Bin Yang SimoneBrethauer Jaclyn DeMartini Mirvat Ebrik Heather McKenzie Tim Redmond Jian Shi Michael Studer Taiying Zhang Rajeev Kumar Qing Qing
  • 35. Acknowledgments Ford Motor Company The BioEnergy Science Center, a U.S. Department of Energy Bioenergy Research Center supported by the of Biological and Environmental Research Office in the DOE Office of Science DARPA Mascoma Corporation Mendel Biotechnology National Institute of Standards and Technology, award number 60NANB1D0064 USDA National Research Initiative Competitive Grants Program, contract 2008-35504-04596 US Department of Energy Office of the Biomass Program, contract DE- FG36-07GO17102 The University of California at Riverside The University of Massachusetts, Amherst Numerous past and present students, coworkers, and partners who make our research possible 35
  • 36. Questions??? 36

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