Thermochemical Conversion of Biomass to Advanced Biofuels at the DOE. S-1041 Conversion Technologies for Biofuels Symposium

Transcription

1 Thermochemical Conversion of Biomass to Advanced Biofuels at the DOE S-1041 Conversion Technologies for Biofuels Symposium Jonathan L. Male August 3, 2010

2 Department of Energy Priorities and Goals Advancing Presidential Objectives "Developing the next generation of biofuels is key to our effort to end our dependence on foreign oil and address the climate crisis -- while creating millions of new jobs that can't be outsourced. With American investment and ingenuity -- and resources grown right here at home -- we can lead the way toward a new green energy economy." Secretary of Energy Steven Chu Science & Discovery Connecting basic and applied bioscience Conducting breakthrough R&D: Advances in enzymes and catalysis Engineering of new microorganisms Novel sustainability indicators Clean, Secure Energy Developing & demonstrating cellulosic and advanced biofuels to meet RFS Economic Prosperity Creating 50 to 75 jobs per new biorefinery Creating major new energy crop markets Reinvigorating rural economies Climate Change Reducing GHG emissions by 60% with advanced biofuels (relative to gasoline) 2

3 EISA Mandated Production Targets Renewable Fuel Standard (RFS) in the Energy Independence and Security Act (EISA) of 2007 EPAct BGY cap on conventional (starch) biofuel Advanced Biofuels (include cellulosic biofuels other than starch-based ethanol) Production Targets (Billions of Gallons) Ethanol & Biodiesel Conventional (Starch) Biofuel Biodiesel Cellulosic Biofuels Other Advanced Biofuels Energy Independence and Security Act defines Advanced Biofuel as renewable fuel, other than ethanol derived from corn starch, that has lifecycle greenhouse gas emissions that are at least 50 percent less than baseline lifecycle greenhouse gas emissions. Cellulosic ethanol technology is important to reaching the 2022 EISA target, however, other advanced biofuels will be needed to aid in this endeavor. 3

4 Strategic Focus Feedstock Supply Biofuels Production Biofuels Distribution Biofuels End Use Expanding and diversifying the portfolio to include renewable hydrocarbon fuels Leveraging bio- and thermo-chemical conversion technology developments from cellulosic ethanol to other advanced biofuels as well as products and power Deploying first-of-a-kind facilities and encouraging strong industry partnerships Program Targets: (At a modeled cost for mature technology) $1.76/gallon cellulosic ethanol by 2012 $2.85/gallon renewable gasoline by 2017 $2.84/gallon renewable diesel by 2017 $2.76/gallon renewable jet by 2017 Crosscutting Activities Analysis, Sustainability, Strategic Partnerships, Stakeholder Communications and Outreach 4

5 Exploring Routes to Convert Biomass Feedstock Production & Logistics Energy crops Forest Residue Agricultural wastes Algae Integrated Biorefineries Biochemical Conversion Pretreatment & Conditioning Enzymatic Hydrolysis Enzyme Production Thermochemical Conversion Fast Pyrolysis Gasification Lipid (Oil) Extraction Liquid Bio-oil Syngas Algal Oil Sugars Distillation Fermentation By-Products Wastes/Residue Upgrading Zeolite Cracking Hydrogenolysis Fischer Tropsch Alcohol Synthesis Transesterification Fractionation R E F I N I N G DDGS Lignin (for power) Ethanol Butanol Olefins Gasoline Diesel Others Research on multiple conversion pathways aims to improve the efficiency and economics of bioenergy production. 5

6 Biofuels Use in Transport Sector Fuel Consumption in the U.S. in 2008 and 2030 (billion gallons/yr) Motor gasoline Diesel Jet fuel Cellulosic ethanol displaces light duty gasoline fraction only Heavy duty/diesel and jet fuel substitutes are needed to displace other components of the barrel Source: Energy Information Administration, Petroleum Explained and AEO2009, Updated (post-arra), Reference Case. 6

7 First Need Abundant, Low Cost Feedstock Dry Herbaceous Agriculture Residues/Crops at less than 15% moisture Energy Crops Wet, Dry, and Woody Woody Forest resources and woody energy crops Strategies to increase feedstock amounts that can be sustainably harvested Develop optimal-performing systems integrating feedstock development, production, and conversion components Economic assessment of production costs, including logistics Feedstock quality designed for optimal conversion efficiency 7

8 Feedstock Logistics Ongoing feedstock logistics projects are developing systems to better handle and deliver high tonnage biomass feedstocks (August 2009 awards) Agco Corporation of Duluth, GA (up to $5 million) for agricultural residues Auburn University of Auburn, Alabama (up to $4.9 million) for woody biomass FDC Enterprises Inc. of Columbus, Ohio (up to $4.9 million) for energy crops Genera Energy, LLC of Knoxville, Tennessee (up to $4.9 million) for energy crops The SUNY College of Environmental Science and Forestry of Syracuse, New York (up to $1.3 million) for woody biomass Deployable Process Demonstration Unit (PDU) to bridge gap between producers and refineries The PDU will allow biorefinery partners to test supply system concepts and reduce feedstock supply risks and allow equipment partners to test new designs and deploy new technologies in the context of an integrated supply system. Will produce engineered feedstocks that meets commodity-scale performance metrics and advanced conversion characteristics. 8

9 Torrefaction Thermal treatment and stabilization process ºC, ~atm pressure, no oxygen Low heating rate < 50 ºC/min minute residence time Advantages Higher energy density Lower O:C More Stable Low moisture Hydrophobic Easier to process, more friable, less fibrous 50-85% reduction in grinding power reported Minimizes coke forming precursors Includes acetic acid of concern in pyrolysis oil White Oak White Oak 220ºC treatment White Oak 270ºC treatment 9

10 Thermochemical Conversion Gasification Current Target By 2012, the gasification-to-ethanol process will achieve a conversion cost of $0.86 per gallon of ethanol ($1.28/GGE, 2007$s, modeled) Major Changes Modest effort in the production of Fischer-Tropsch alkanes After 2012 leverage R&D to focus solely on infrastructure compatible fuels Key Challenges Syngas clean up and conditioning Fuel synthesis Operate fully integrated process for > 200 hours 10

11 Gasification: State of Technology and Projection Minimum Ethanol Selling Price ($/gal) $3.47 $3.57 $2.40 $2.26 $1.90 $1.70 $1.57 Feedstock Contribution ($/gal) $1.58 $1.58 $1.05 $0.95 $0.80 $0.73 $0.71 Conversion Contribution ($/gal) $1.89 $1.89 $1.35 $1.31 $1.10 $0.97 $0.86 Ethanol Yield (Gallon/dry ton) Mixed Alcohol Yield (Gallon/dry ton) Feedstock Feedstock Cost ($/dry ton) $67.55 $67.55 $63.50 $58.20 $54.20 $51.80 $50.70 Syngas Generation Syngas Yield (lb/lb dry feed) CH 4 Concentration in raw syngas(mol %-dry basis) Syngas Cleanup and Conditioning Tar Reformer CH 4 conversion (%) Tar Reformer Benzene conversion (%) Tar Reformer Total Tar conversion (%) Tar Reformer Exit CH 4 concentration (mol %) Catalytic Fuel Synthesis Compression for fuel synthesis (psia) Single pass CO conversion (%) Overall CO conversion (%) CO Selectivity to alcohols - CO 2 free basis (%) Total Alcohol Productivity (g/kg/hr) Major Focus (Single Pass) Major Focus

12 Catalytic Tar Cracking /Methane Reforming Challenges Fundamental Challenge: Untreated syngas from biomass contains contaminants (S, Cl, P containing gases) that poison tar cracking/methane reforming catalysts. General Approaches: Reduce contaminants from hot untreated gas before catalytic tar cracking/methane reforming Frequent/continuous regeneration of existing hot gas sorbents Development of contaminant resistant hot gas sorbents for periodic regeneration Crack tars/reform methane in hot untreated syngas with contaminants present Frequent/continuous regeneration of existing catalysts Development of contaminant resistant catalysts for periodic regeneration Develop a process utilizing some combination of the approaches 12

13 Syngas Cleanup: Contaminant Reduction Rationale CH 4 Conversion (%) To remove H 2 S, a catalyst poison, at a temperature close to those of gasification and tar reforming (> 700 C) Inexpensive S sorbents would increase reforming catalyst lifetime H 2 S Introduction Sorbent/catalyst Time (min) Catalyst Sorbent Accomplishments Developed a manganese based sorbent that removes H 2 S from 1,000 to 1 ppmv in simulated biomass syngas Demonstrated with real biomass syngas produced from corn stover Energy & Fuels, 23: (2009). 13

14 Syngas Cleanup: Continuous Reforming Catalyst Regeneration Catalyst Regeneration Strategy Reformed Syngas Methane Conversion During Continuous Regeneration 100 Spent Catalyst % CH 4 Conversion Syngas 880 C 80 ppm H2S, 890 C 160 ppm H2S, 925 C 160 ppm H2S, 32,000 mg/nm3 tar, 910 C Steam Air Catalyst Circulation Experimental Condition Hypothesis: Ni-alumina reforming catalyst is regenerable after reaction with H 2 S in raw syngas H 2 Regenerated Catalyst Dirty Syngas Industrial collaborator evaluated NREL catalyst for 100 h of tar reforming simulated syngas containing H 2 S and SO 2 CH 4 conversion maintained at > 92% under recirculating regenerating conditions 14

15 Fuel Synthesis Catalysts Energy, ev Catalyst Characterization (XRD, TEM, XPS, BET, Etc.) provides snapshots of fresh, activated and spent catalysts CRADA with DOW and Others To develop improved performance in MAS catalysts Rh:Mn = 50:0 Rh:Mn = 49:1 Rh:Mn = 47:3 Active sites for CH X +CO coupling Computational Chemistry to Improve Catalyst Performance Uses quantum theory to explain catalyst behavior Morphological changes of catalyst Interaction of catalyst with reactants, etc Journal of Catalysis, 271, , (2010). 15

16 Thermochemical Conversion Fast Pyrolysis Current Target By 2017, a biomass-based thermochemical route that produces gasoline and diesel blendstocks and will achieve a conversion cost of $1.56 per gallon of total blendstock ($1.47/GGE, 2007$, modeled). Key Challenges Stabilizing bio-oil for > 6 months under ambient conditions Fuel processing Operating fuel processing catalysts for > 1000 hours 16

17 Fast Pyrolysis: State of Technology and Projections $6.02/gge $4.71/gge $3.51/gge $1.56/gge 2009 SOT 2010 Projection 2012 Projection 2017 Projection Conversion Contribution ($/gal gasoline) $6.30 $4.92 $3.51 $1.56 Conversion Contribution ($/gal diesel) $6.37 $4.99 $3.57 $1.56 Conversion Contribution ($/gge total fuel) $6.02 $4.71 $3.38 $1.48 Feed Drying, Sizing, Fast Pyrolysis ($/gal total fuel) $0.54 $0.53 $0.52 $0.34 Upgrading to Stable Oil ($/gal total fuel) $4.69 $3.34 $2.01 $0.46 Fuel Finishing to Gasoline and Diesel ($/gal total fuel) $0.30 $0.29 $0.29 $0.12 Balance of Plant ($/gal total fuel) $0.82 $0.81 $0.74 $0.64 Current stakeholders: NREL, PNNL, INL, ORNL, Univ. of Massachusetts Amherst, Univ. of Purdue, RTI, UOP, Iowa State Univ., Virginia Polytechnic Institute. 17

18 Bio-oil Technical Challenges Pyrolysis occurs at ambient pressure, inert atmosphere and C at reaction times approaching 0.5s Gives relatively high oil yields approaching 70% by weight Fast pyrolysis oil (bio-oil) however has many undesirable properties: High water content: wt% High O content: 35-40% High acidity; ph = 2.5, TAN > 100 mg KOH/g oil Unstable (phase separation, reactions) Low HHV: MJ/kg Distillation residue: up to 50 wt % Czernik & Bridgwater,

19 Gasoline/Diesel Prospects Bioderived fuel from corn stover spinning band distillation 54% in gasoline range IBP-193 C Gasoline Octane number RON+MON/2=89 35% in diesel range C Cetane number % heavies >325 C likely partially converted feed Deoxygenated bio-oil produces a high quality gasoline component, lower quality diesel and a jet blending component Corn stover or mixed wood derived bio-oil can be upgraded to jet range hydrocarbons: 45 65% depending on feed source and process conditions from: Timothy Brandvold, UOP LLC, Pyrolysis Oil to Gasoline presented at the Thermochemical Portfolio Alignment and Peer Review April 15, 2009, Denver, CO 19

20 Distributed Pyrolysis and Centralized Bio-Oil Processing Corn Stover Deoxygenate Biomass Pyrolysis Mixed Woods Stabilization Gasoline Diesel Jet Chemicals Holmgren, J. et al. NPRA national meeting, San Diego, February This work was developed by UOP, Ensyn, NREL and PNNL and is for fully upgraded bio-oil (TAN < 2, oxygen content < 1 wt%) that is refinery ready 20

21 NABC Infrastructure Compatibility Strategy Biomass Refinery-Ready Intermediates Finished Fuels and Blendstocks Insertion Point #1 Insertion Point #2 Insertion Point #3 Crude Oil Refining: 750 refineries 85M BBL of crude refined daily 50M 21 BBL transport fuels Atmospheric and Vacuum Distillation Gas L Naphtha H Naphtha LGO VGO Atm. Res. Vac. Res. Reform FCC Alky/Poly HT/HC Coker Existing Refinery Infrastructure Drop-In Fuels Gasoline Jet Fuel Diesel Fuel Terminal Tank farm 21

22 Future Thrusts Continued bio-intermediate quality improvement and biofuel synthesis integration Continued conditioning/stabilizing syngas and bio-oil Continued drive for higher activity and selectivity, robust catalysts Moving towards a diverse portfolio of technologies for infrastructure compatible biofuels, requiring a need to develop: Other thermochemical conversion routes Catalysts: New routes need to be analyzed for potential research New targets must be developed Analysis of different entry points of bio-intermediates into existing petroleum refineries 22

23 Recent Funding Opportunities Upgrading of Biomass Fast Pyrolysis Oil (Bio-oil) Funding: Up to $11,000,000 total Close Date: 07/09/2010, Applications under review This funding is to develop integrated upgrading processes of bio-oil. Biomass Research and Development Initiative Funding: up to $33 million Close Date: 07/13/2010, Applications under review This is a joint effort between the U.S. Department of Agriculture and the U.S. Department of Energy to support funding for research and development of technologies and processes to produce biofuels, bioenergy and high-value biobased products Development of Methodologies for Determining Preferred Landscape Designs for Sustainable Bioenergy Feedstock Production Systems at a Watershed Scale Funding: Approximately $5,000,000 Close Date: 07/16/2010, Applications under review This funding is for research focused on sustainable production of large quantities of non-food biomass for bioenergy Upcoming announcements are expected on biopower and additional broad bioenergy areas of focus in 2011 For More Information visit: or 23

24 Biopower Launch a new DOE initiative to accelerate, develop and deploy advanced biopower technologies over the next six years. Initiative will establish partnerships with industry and support efforts to: Conduct R&D on advanced pretreatment and conversion technologies by 2013 increase overall efficiency improve environmental performance decrease cost of biopower electricity Support pilot scale projects up to 10 MW Demonstrate utility scale, biomass repowering and high percentage co-firing ( 25% biomass) with coal by 2016 up to 100 MW 24

25 Information Resources Office of Biomass Program, EERE Info Center - www1./informationcenter Alternative Fuels Data Center - Bioenergy Feedstock Information Network - Biomass R&D Initiative Grant Solicitations - Office of Science - Loan Guarantee Program Office - Loan Guarantee Final Rule

26 Approach 26

27 Key Milestones FY10 Thermochemical Conversion End Of Year Joule Target Achieve a modeled ethanol price of $1.90/gallon (conversion cost $1.10/gallon) for thermochemical gasification of biomass feedstocks followed by mixed alcohol synthesis and ethanol separation, by demonstrating technology at either the bench or pilot-scale. The economics will be based on 2007 dollars with a feedstock cost of $54.20/dry ton. Quarterly Milestones By December 31, 2008, demonstrate 90% reduction in H 2 S concentration at > 500 C and GSHV of >3000 h -1 with high temperature sulfur sorbent combined with tar reforming to achieve biomass derived syngas cleanup. By March 31, 2009, demonstrate bench scale reactor(s) system operation and determine baseline performance for mixed alcohol synthesis catalyst(s). By June 30, 2010, achieve a single-pass CO conversion with a selectivity of at least 40% to C 2 + oxygenates while retaining a space-time-yield of at least 800 g/kg cat /hr and an 80% selectivity of all oxygenates to alcohols. 27

28 Gasoline Analyses From Two Step Hydroprocessing Hydroprocessed Bio-oil (from Mixed Wood) Petroleum Gasoline Min Max Typical Paraffin, wt% Iso-Paraffin, wt% Olefin, wt% Naphthene, wt% Aromatic, wt% Oxygenate, wt% 0.8 The carbon recovery based on bio-oil was about 50%. Holmgren, J. et al. NPRA national meeting, San Diego, March

29 Our Commitment to Sustainability Develop and invest in the resources, technologies, and systems needed for biofuels to grow in a way that enhances the health of our environment and protects our planet. Environmental Sustainability Economic Sustainability Social Sustainability Feedstock Supply Biomass-to-Bioenergy Supply Chain Conversion Distribution End Use Field-based research to evaluate nutrient and carbon cycling Collecting biomass physical and chemical properties impacting land use sustainability Minimizing water consumption and air pollution, maximizing efficiency Monitoring and improving the carbon footprint of new facilities; promoting coproduct utilization and fully integrated systems Ensuring minimal greenhouse gas emissions and avoidance of negative impacts on human health Cross-cutting Life cycle analysis of water consumption and greenhouse gas emissions; land use change modeling; water quality analysis of biofuels 29

30 Thermochemical Conversion R&D Competitive Partnerships Thermochemical Conversion (up to $7.75 million) Objective: Syngas clean up validation Goal: Create a syngas that meets the cleanliness specifications of existing synthesis processes from widely available biomass. All applicants selected FT Fuels as the biofuel target. Demonstrate integration of gasification and catalyst development Awardees: RTI, GTI, Emery Energy, Iowa State Univ., Southern Research Institute Award Duration: Pyrolysis Oil Stabilization (up to $7.5 million) Objective: Stabilizing bio-oil prior to upgrading Goal: Removing char, lowering the oxygen content, and reducing the acidity of pyrolysis oil Awardees: UOP, Iowa State, Virginia Polytech., RTI, Univ. Mass, Amherst Award Duration:

31 Transportation Options For Biofuels MTG Ag residues, (stover, bagasse) Both Biochemical and Thermochemical Platforms have an Important Role to Play 31

32 National Advanced Biofuels Consortium Project Objective Develop cost-effective technologies that supplement petroleum-derived fuels with advanced drop-in biofuels that are compatible with today s transportation infrastructure and are produced in a sustainable manner. ARRA Funded: - 3 year effort - DOE Funding $33.8M - Cost Share $12.5M Total $46.3M Consortium Leads National Renewable Energy Laboratory Pacific Northwest National Laboratory Consortium Partners Albemarle Corporation Amyris Biotechnologies Argonne National Laboratory BP Products North America Inc. Catchlight Energy, LLC Colorado School of Mines Iowa State University Los Alamos National Laboratory Pall Corporation RTI International Tesoro Companies Inc. University of California, Davis UOP, LLC Virent Energy Systems Washington State University 32 32

33 National Renewable Energy Lab & Pacific Northwest National Lab Albemarle Corp., Amyris Biotechnologies, Argonne National Laboratory, BP Products NA, Catchlight Energy, Colorado School of Mines, Iowa State University, Los Alamos National Lab, Pall Corp., RTI International, Tesoro Companies, University of California, Davis, UOP, Virent Energy Systems, Washington 33 State University

34 Algal Biofuel Systems: Technical Challenges Biology and Cultivation Energy efficient harvesting and dewatering systems Biomass extraction and fractionation Product purification A gasifier being used by a NAABB partner to convert algal biomass to fuels Cultivation system design Temperature Control Invasion and fouling Cultures Growth, stability, and resilience Input requirements CO 2, H 2 O sources, energy Nitrogen and phosphorous Siting and resources Biomass Harvesting and Recovery A nano-membrane filter being developed by a NAABB partner. Process optimization Thermochemical Biochemical Fuels characteristics Co-Products Conversion and End-use 34

35 Biofuels Consortia: Algal Biofuels R&D Breaking down critical barriers to the commercialization of algae based biofuels such as green aviation fuels, diesel, and gasoline that can be transported and sold using today s existing fueling infrastructure. National Alliance for Advanced Biofuels and Bioproducts Sustainable Algal Biofuels Consortium Consortium for Algal Biofuels Commercialization Cellana, LLC Consortium 35

36 National Alliance for Advanced Biofuels and Bioproducts Project Objective Investigate and integrate multiple approaches to meet the central challenges of feedstock production, handling logistics, and conversion in order to lower costs of algal biofuels. Funding - 3 year effort Recovery Act/DOE Funding $49M Cost Share $25M Total $74M 36

37 Development and Commercialization Value Chain 37

38 National Laboratory Biomass Core Capabilities Oak Ridge National Laboratory (ORNL) Multiple programs focused on establishing energy crops Feedstock supply Idaho National Laboratory (INL) Feedstock logistics Feedstock harvesting and delivery systems National Renewable Energy Laboratory (NREL) Integrated biochemical biorefinery technology Thermochemical gasification technology Argonne National Laboratory (ANL) Molecular separations Life Cycle Analysis (LCA) Pacific Northwest National Laboratory (PNNL) Fungal systems technology Catalysts development 38

39 Maximizing the Impact of Biomass in the Pacific Northwest New 57,000 ft 2 laboratory dedicated May 8,2008 Joint effort with Washington State University about 15 WSU staff including four professors led by Dr. Birgitte Ahring 50 PNNL research staff $11 million in state-of-the-art equipment Combinatorial catalysis, autoclave reactors, continuous flow reactors Proteomics line, batch and continuous fermentors High bay with pyrolysis and gasification units Complete analytic support 39

40 Integrated Biorefineries Feedstock Conversion Intermediate Conversion Product Performer Agricultural Residues biochemical gasification pyrolysis sugar syngas oil fermentation catalysis ethanol diesel Abengoa, Poet, Verenium, ADM Ineos REII Forest Resources biochemical gasification pyrolysis sugar syngas oil fermentation catalysis ethanol gasoline diesel jet fuel Lignol, Mascoma, Pacific Ethanol RSA, API, Zeachem, Blue Fire Range Fuels Haldor Topsoe Clear Fuels New Page, Flambeau GTI, UOP Energy Crops / Grasses/ biochemical Sugar fermentation ethanol diesel succinic acid ICM, Logos Amyris Myriant 40

41 Integrated Biorefineries Feedstock Conversion Intermediate Conversion Product Performer open pond oil catalysis diesel jet fuel Sapphire Algae catalysis diesel jet fuel Solazymes Closed bioreactor oil transesterification biodiesel metathesis diesel jet fuel Elevance ethanol Algenol MSW gasification syngas catalysis ethanol Enerkem 41

42 Locations of Integrated Biorefinery Projects For more information, visit: 42