Hydrocarbon Drop-In Biofuels Engine Research Center University of Wisconsin-Madison June 8, 2011

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1 PNNL-SA Hydrocarbon Drop-In Biofuels Engine Research Center University of Wisconsin-Madison June 8, 2011 John Holladay Pacific Northwest National Laboratory PO Box 999, MSIN: P8-60, Richland, WA

2 Energy Security and Market Supply & Demand Balance Dr. Paul Bryan At low % of total market supply & demand, refiners can adapt As % blend increases, issues arise in refining and blending: Refinery balance (light / heavy, H 2, octane, vapor pressure, ) Petrochemical feedstocks (naphtha, pen-hex, BTX, light paraffins & olefins, ) Source: Energy Information Administration, Oil: Crude Oil and Petroleum Products Explained and AEO2009, Updated February 2010, Reference Case. Ethanol competes with gasoline, batteries, H 2, and mass-transit, while only liquid fuels compete in most diesel & jet markets

3 DOE-EERE Advanced Biofuels Consortia NABC Lignocellulosics, NAABB Algae Texas A&M Pecos Site Solix Biofuels Coyote Gulch

4 Slide 4 National Alliance for Advanced Biofuels and Bioproducts

5 Natural Oils Options like Ecofining: Product is a High Quality Pure Hydrocarbon HO O Free Fatty Acid CH 3 H 2 CO 2 + H 3 C CH 3 H 2 O + H 3 C CH 3 Feed HC O O O O O Reactor System O Separator Triglyceride Acid Gas Removal Water CH 3 CH 3 CH 3 Make-up Hydrogen CO 2 CO 2 H 2 O Propane & Light Ends Green Naphtha or Jet Green Diesel Product H H 3 C 3 C CH 3 CH + 2 H 3 C H 3 C CH 3 Propane Straight Chain Paraffins % UOP Catalyst CH 3 CH 3 Green Diesel CH 3 CH CH 3 H 3 C 3 H 3 C + H 3 C CH 3 + CH 3 CH 3 H 3 C CH 3 & Green Naphtha UOP

6 National Advanced Biofuels Consortium The National Advanced Biofuels Consortium (NABC) is a collaboration among U.S. Department of Energy national laboratories, universities, and private industry that is developing technologies to produce infrastructurecompatible, biomass-based hydrocarbon fuels. NABC : For Open Distribution

7 Crude Oil Refinery: Infrastructure Conversion Picture courtesy of

8 NABC Strategies and Technologies Converting biomass into infrastructure - compatible materials

9 Fermentation of Lignocellulosic Sugars ANY FEEDSTOCK INDUSTRIAL SYNTHETIC BIOLOGY PLATFORM RENEWABLE CHEMICALS AND FUELS Team led by Amyris

10 FLS Process Strategy Overview hydrolysate YEAST CELL Mevalonate Pathway Farnesene Farnesene Synthase Diesel & Chemical Precursor [1] Cane juice [2] Fermentation broth [3] Separations [4] Purification [1] [2] [3] [4]

11 Results: Dilute Acid/Enzyme Hydrolysis of Pine Acid Pretreated Low severity: 190 C, 3 minutes, 0.63% sulfuric acid in liquid Acid Pretreated High severity: 210 C, 3 minutes, 1.0% sulfuric acid in liquid

12 Catalysis of Lignocellulosic Sugars Team led by Virent

13 Catalysis of Lignocellulosic Sugars Process options to produce hydrocarbons from lignocellulosic sugars

14 Catalysis of Lignocellulosic Sugars BioReformate Sugar Hydrolysate

15 Heating biomass can give a bio-oil or synthesis gas Heat Vapor Biomass Bio- Char Syn Gas Bio- Oil Fast Pyrolysis (reference) Ambient pressure T = C Residence times 0.5 s Oil yields around 70% (wt%) Fast pyrolysis oil: High water content: 15-30% High O content: 35-40% High acidity; ph = 2.5, TAN > 100 mg KOH/g oil Unstable (phase separation, reactions) Low HHV: MJ/kg

16 Fast pyrolysis oil is converted to fuels in a 2-step process (reference case) H 2 light products Hydroprocessed Bio-oil (from Mixed Wood) Petroleum Gasoline H 2 O HT HC aqueous byproduct medium products heavy products Min Max Typical Paraffin, wt% Iso-Paraffin, wt% Olefin, wt% Naphthene, wt% Aromatic, wt% Oxygenate, wt% 0.8 Holmgren, J. et al. NPRA national meeting, San Diego, March The carbon recovery based on bio-oil was about 50%

17 Hydroprocessed Bio-oil makes jet fuel range fuels percent distilled % 42.4% jet batch 1 batch 2 20 naphtha temperature, degrees Celsius (corrected to 1 atm)

18 Catalytic Fast Pyrolysis UOP leads the team Replace sand (heat transfer medium) with catalysts

19 Catalytic Fast Pyrolysis Standard Fast Pyrolysis Catalytic Fast Pyrolysis

20 Hydropyrolysis RTI Team Lead Add H 2 (reactive gas) during pyrolysis RTI s Transport Reactor System

21 Hydropyrolysis Reactive gas to cap intermediates in pyrolysis vapor Catalytically enhanced hydrogen transfer to reduce oxygen content Use of process modeling to explore commercial concepts

22 Hydropyrolysis -Preliminary Screening Results Improved hydrocarbon yields through effective catalytic hydrogen-transfer Gas / P (psi) Catalyst Char Yield (wt%) He / 400 none 10.5 H2 / 400 none 21.0 H2 /400 2wt% DCat-CS1 21.8

23 Hydrothermal Liquefaction Slow pyrolysis in ph-moderated, pressurized water Wet biomass H 2 Hydrothermal Liquefaction Catalytic upgrading Liquid hydrocarbons ~350ºC, 200 atm, biomass slurry in water minutes solids PNNL Team Lead

24 Hydrothermal Liquefaction biomass slurry in water ~350ºC, 200 atm, residence time of minutes

25 Hydrothermal Liquefaction Preliminary Results Wood Wet feed (9.4 wt%) feed operated for 8 temp and pressure 45 g/h separated oil; 30% mass oil yield, 53% on carbon basis 10.9% oxygen on dry basis, 30 TAN, 9.8% moisture 0.2% nitrogen, 0.01% sulfur, 0.03% ash, 0.34% solids 12% carbon conversion to gas gas 82% CO 2, 12% H 2, 6% CH 4 and higher hydrocarbon 35% carbon in aqueous, 4.6 ph effluent; 44,000 ppm COD Corn Stover 11.1 wt% double wet grind feed operated for 8 similar conditions 51 g/h separated oil ~1 wt% nitrogen in oil

26 Analysis Team Feedstock Composition Operating Conditions Measured Conversion Yields Process Model in Aspen Plus Process Economics using Discounted Cash Flow Analysis with Capital and Operating Costs Flow rates Minimum Fuel Selling Price Cost $ R&D TEA LCA Fuel Product Yield gal

27 Critical Issues Addressed Critical Success Factors Acceptable fuels & intermediates quality demonstrated Potential for commercial readiness demonstrated Reduced carbon footprint compared to fossil based fuels Carbon & energy efficiency maximized Capital and operating costs minimized Catalyst/organism robustness Toxicity levels < EPA limits Example Biochemical Targets (end Stage II) Example Thermochemical Targets (end Stage II) TAN<0.5, O content < 0.2 Final products show potential to meet ASTM standards Intermediates pass 60 day stability test Process is ready to pilot based on MB closure, scale/reproducibility of data and well-defined operations Process achieves >50% GHG reduction compared to gasoline, jet or diesel benchmark Carbon and energy efficiency demonstrated to be >50% -Reduction in cellulase cost contribution>50% -Feed concentration to reactor>50% -95% conversion of carbohydrate portion -Inhibitory compounds identified/mitigated Reactor RT <5 sec (CFP) Reactor P < 500 psig (HYP) Lifetime >1 year Loading <5:1 Analytical methods developed to identify compounds 27

28 General Conclusion Shift of emphasis at DOE (EERE) toward the fuels that should be produced from biomass resources (emphasis on replacing the whole barrel of oil NABC and NAABB leading in technology development (NAABB has a feedstock focus on algal oils and biomass; NABC a conversion focus) NABC emphasis on integration with refinery use of infrastructure in place to make and deliver those fuels into our vehicle fleet today Six technologies are being examined, pilot ready technology will be delivered at the conclusion

29 General Conclusion Shift of emphasis at DOE (EERE) toward the fuels that should be produced from biomass resources (emphasis on replacing the whole barrel of oil NABC and NAABB leading in technology development (NAABB has a feedstock focus on algal oils and biomass; NABC a conversion focus) NABC emphasis on integration with refinery use of infrastructure in place to make and deliver those fuels into our vehicle fleet today Six technologies are being examined, pilot ready technology will be delivered at the conclusion

30 Questions Special Acknowledgement to National Advanced Biofuels Consortium (NABC) Led by the National Renewable Energy Laboratory Tom Foust (PI) National Alliance for Advanced Biofuels and Bioproducts Led by Danforth Plant Sciences Center / Los Alamos National (NAABB) Jose Olivares (PI)