Production of Drop-In Hydrocarbon Fuels from Cellulosic Biomass Track 3: Advanced Biofuels and Biorefinery Platforms Session 2: Monday, December

Transcription

1 Production of Drop-In Hydrocarbon Fuels from Cellulosic Biomass Track 3: Advanced Biofuels and Biorefinery Platforms Session 2: Monday, December 9-10:30 AM - 12:00 PM Moderator: Thomas Foust, National Renewable Energy Laboratory Thomas Foust, National Renewable Energy Laboratory Jesse Q. Bond, Syracuse University Charles Cai, University of California Riverside Brittany Syz, Oberon Fuels

2 Aqueous Platforms for Conversion of Cellulosic Biomass Into DropIn Hydrocarbon Fuel Precursors Charles Cai*, Taiying Zhang, Rajeev Kumar, and Charles E. Wyman Chemical and Environmental Engineering Department and Center for Environmental Research and Technology (CE-CERT) University of California Riverside Riverside, California Pacific Rim Summit on Biotechnology and Bioenergy San Diego, California December 9, 2013

3 Acknowledgments 3 Sun Grant Initiative (NO. T0013G- H/11W-DOT-021) Fellowship from University of California Transportation Center (UCTC) DARPA through University of Massachusetts Ford Motor Company Center for Environmental Research & Technology (CE-CERT), University of California, Riverside for facilities

4 Presentation Outline 4 Motivation for fuel production from biomass Chemistries of fuel precursor (FP) formation Opportunities and limitations of aqueous biomass conversion Our research thrusts to enhance FP production 1. Biphasic solvent system enhanced furfural and 5- HMF production 2. Single phase co-solvent enhanced furfural and levulinic acid production Closing thoughts

5 Aqueous Processing of Cellulosic Biomass to Fuel Precursors 5 A renewable alternative for liquid transportation fuel is needed to reduce greenhouse gas emissions and long term sustainability of the transportation sector Lignocellulosic biomass is the only sustainable platform for low-cost liquid fuel production Fuel precursors: Sugars and dehydration products Figure from EERE: <

6 Distribution of Lignocellulosic Biomass Cell Wall Components 6 Cellulose ~35-50% by weight Primarily composed of glucan Hemicellulose Heterogeneous structure ~15-30% by weight Often predominately xylan Lignin/other ~15-30% by weight The acid insoluble portion is commonly termed Klason lignin Smith, J.C., DOE. SciDAC review. <

7 Biorefineries Could Produce Multiple Products from Lignocellulosics 7 Figure adapted from C. E. Wyman. ACS Conference. Washington, DC. (1990)

8 Biorefineries Could Produce Multiple Products from Lignocellulosics 8 Figure adapted from C. E. Wyman. ACS Conference. Washington, DC. (1990)

9 Production of Fuel Precursors from Cellulosic Biomass 9 BP 80C RON 86 93C C C 130 9

10 Degradation products are expected from highly reactive intermediates 10 HO HO OH O OH n OH HO O O H+ H+ H+ HO OH O H OH HO O * HO OH O OH Xylan Xylose Furfural Formic acid HO O OH OH O O * n OH H+ H+ HO HO OH O Glucan Glucose 5-HMF OH HO O Levulinic acid + Formic acid Adapted from Weingarten, R. et. al Green Chem., 2010, 12, O H+ Highly reactive species O O OH + H O OH

11 Current and Past Processes for Furfural Production 11 Process Process Type Operating Temperat ure ( C) Quaker Oats Batch/Aqueou s Quaker Oats Continuous/A queous Huaxia/Westp ro Vedernikovs Zeitsch/Supra Yield Continuous/A queous Continuous/A queous Continuous/A queous Catalyst Substrate Furfural Yield (% theoretical) Co-products 153 H 2 SO 4 Oat Hulls <50% N/A N/A H 2 SO 4 Bagasse 55% N/A H 2 SO 4 Corn Cobs 35-50% Methyl alcohol, acetone, acetic acid, levulinic acid 188 H 2 SO 4 Wood chips 75% Acetic acid, ethanol 240 H 2 SO 4 N/A 50-70% N/A CM Cai, T Zhang, R Kumar, CE Wyman Journal of Chemical Technology and Biotechnology. 89 (1) 2-10

12 Quaker Oats Batch Process 1. Mixer, 2. Reactor, 3. Screw Press, 4. Secondary Steam Generator, 5. Azetropic Distillation Column, 6. Decanter, 7. Condensers, 8. Recovery Column for low Boilers, 9. Furfural Dehydration Column. HPS=High pressure Steam, LPS=Low Pressure Steam 12

13 Continuous Furfural Production from Bagasse in Belle Glade, Florida

14 Belle Glade Reactor Tubes

15 15 Issues with Current Technology Competition from low-priced Chinese furfural Equipment and particularly feeder lifetime High energy cost t-steam/t-furfural for reaction and furfural recovery Limited furfural yields (<60% molar yields) Low value use of cellulose: mostly burned

16 Materials and Methods 16 Maple wood chips and corn stover (1mm particle size, air dried) Sulfuric acid catalyst Organic solvents used: Methyl Isobutyl Ketone (MIBK) Tetrahydrofuran (THF) Reactor: 1 L Hastalloy Parr reactor Analysis by HPLC with Aminex HPX-87H/P column

17 yield (%) Furfural Yields in Typical Aqueous Reaction with Sulfuric Acid Furfural Furfural Xylose Xylose Glucose Xylose Levulinic 5-HMF Furfural HMF 5-HMF Reaction time (min) Levulinic acid Levulinic

18 yield (%) Major C6 Product is Glucose Glucose Glucose HMF 5-HMF Reaction time (min) Glucose Levulinic 5-HMF Levulinic acid Levulinic

19 Kinetics Limit Co-Production of Fuel 19 Precursors from 5 and 6 Carbon Sugars Hemicellulose is more readily hydrolyzed than cellulose LA is more stable product from glucose than 5-HMF Preservation of the least stable FP is crucial to maximize overall yields Two-stage reaction may be beneficial First: Furfural and 5-HMF production Second: LA production From J.P. Lange et. al, ChemSUSChem. (2012). 5:

20 1. Increase Yields with 2 Phase Reaction and Simultaneous Organic Solvent Extraction 20 Immiscible organic solvent, e.g., methyl isobutyl ketone (MIBK) was used Furfural partitions to organic phase Furfural degradation limited in organic phase Furfural solubility in each phase governs degradation Mineral acid remains primarily in aqueous phase for recycle Hydrolysis, dehydration, and decarboxylation reactions require H + Hydrolysis and dehydration occur in aqueous phase MIBK Aqueous 5 wt% maple wood loading based on aqueous phase 20

21 Furfural yield (%) Simultaneous Solvent Extraction by MIBK Improves Furfural Yields % yield Total furfural in in both both phases Total furfural in both phases Reaction condition: 0.1M H 2 SO 4 at 170 o C Furfural in aqueous phase Furfural in organic phase Furfural in organic phase Furfural in aqueous phase Furfural in organic phase Total furfural in both phases Furfural in aqueous phase Reaction time (min) T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3,

22 Yield (%) Simultaneous Solvent Extraction by MIBK Improves 5-HMF Yields Furfural Xylose Glucose Xylose Levulinic 5-HMF Furfural 5-HMF Reaction condition: 0.1M H 2 SO 4 at 170 o C Glucose Levulinic Reaction time (min) 22 T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3,

23 solid from 100g maple wood solid from 100g maple wood Effect of Solvent on Composition of Residual Solids Raw No Solvent other xylan glucan lignin/humins reaction time (min) With Solvent other xylan glucan lignin reaction time (min) Reaction condition: 0.1M H 2 SO 4 at 170 o C T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3,

24 Material Balance: Furfural, HMF, and LA Biphasic furfural production: Parr reactor, 170 o C, 50 min, 0.1M H 2 SO 4, 5% solid loading Biphasic furfural production: Parr reactor, 170 o C, 60 min, 0.1M H 2 SO 4, 5% solid loading 20g raw maple wood, 380g 0.1 N H 2 SO 4 Biphasic FF production Organic solvent Organic solvent Solid residue with aqueous phase: 32.5% yield (53% glucan & 46% lignin) Aqueous phase: acidic Pure lignin residue 14.95% Organic phase: Organic phase: 81.8% furfural, 30.6% 5-HMF, 6.0% LA Organic phase: 41.2% 5-HMF & 24.5% LA Overall furfural yield = 84.3 % Overall 5-HMF yield = 51.3 % Overall levulinic acid yield = 19.0 % Overall C5 sugar and products yield in liquid phase = 88.4 % Overall C6 sugar and products yield in liquid phase = 52.4 % T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3,

25 2. Use of Tetrahydrofuran (THF) as Unique Single Phase Co-Solvent 25 Miscible with water Low boiling point (66 C) facilitates recovery/recycle 4.6% azeotrope with water High affinity for furfural and 5- HMF 21.5 partition coefficient in water High thermal efficiency from a single phase process Dissolves lignin Can be produced from furfural and levulinic acid as co-product THF solution Water solution 5 wt% maple wood loading

26 Levulinic, g/l Furfural, g/l Glucose, g/l Glucose + Xylose, g/l THF Promotes Sugar Dehydration and Enhances FP Production from Maple Wood 26 No THF With THF No THF With THF With THF No THF With THF No THF With THF No THF Conditions: 170C 1% H 2 SO 4, 1:1 THF:Water C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

27 % Yield of theoretical THF is Highly Selective for Furfural and 5- HMF from Different Feedstocks Maple wood Conditions: 170C 1% H 2 SO 4, 1:1 THF:Water Levulinic acid 550% 2 5-HMF 40% % Furfural Levulinic acid Corn stover With THF No THF 466% HMF 59 Furfural C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

28 % Yield of theoretical Increasing Solvent:Water Ratio Can Enhance Co-Production Potential and Biomass Solubilization :3 THF:Water 1:1 THF:Water 3:1 THF:Water 29 Conditions: 170C 1% H 2 SO 4, 1:1 THF:Water Levulinic acid 5-HMF Furfural C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

29 LA yield(%) High Levulinic Acid Production from Hexose- Rich Pretreated Maple Wood Residue % LA yield 2% H 2 SO % H 2 SO 4 1.5% H 2 SO 4 0.5% H 2 SO % H 2 SO 4 1% H 2 SO % H 2 SO 4 2% H 2 SO % H 2 SO 4 4.9% H 2 SO Reaction conditions: 10 wt% pretreated maple wood (hydrothermal) 200 C reaction reaction time (min) C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

30 Substantial Lignin Removal by Co-Solvent System 30 Conditions: 170C 1% H 2 SO 4, 1:1 THF:Water C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

31 Material Balance: High Overall Recovery of FPs with THF Co-Solvent Reaction 31 C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15,

32 THF and MIBK Enhance Furfural Yields and Allow for Unique Co-production Strategies Process Process Type Operating Temperat ure ( C) Quaker Oats Batch/Aqueou s Quaker Oats Continuous/A Huaxia/Westp ro Vedernikovs Zeitsch/Supra Yield MIBK extraction THF cosolvent queous Continuous/A queous Continuous/A queous Continuous/A queous Batch/Aqueou s organic Batch/Aqueou s organic Catalyst Substrate Furfural Yield (% theoretical) Co-products 153 H 2 SO 4 Oat Hulls <50% N/A N/A H 2 SO 4 Bagasse 55% N/A H 2 SO 4 Corn Cobs 35-50% Methyl alcohol, acetone, acetic acid, levulinic acid 188 H 2 SO 4 Wood chips 75% Acetic acid, ethanol 240 H 2 SO 4 N/A 50-70% N/A H 2 SO 4 Corn stover Hard woods H 2 SO 4 Corn stover Hard woods >85% 5-HMF, glucose, lignin >85% Levulinic acid, 5- HMF, glucose, lignin 32 CM Cai, T Zhang, R Kumar, CE Wyman Journal of Chemical Technology and Biotechnology. 89 (1) 2-10

33 Closing Thoughts Traditional aqueous catalytic conversion of lignocellulose is limited by low yields and inefficient production Viable catalytic pathways for production of gasoline, jet, and diesel range fuels from biomass-derived sugars enable advancement of integrated production of fuel precursors (FPs) from biomass Complexity of biomass and kinetics of sugar breakdown provide interesting limitations to achieving integrated co-production of FPs. Our high-yield biomass-to-fp strategies: Biphasic extraction of furfural and 5-HMF using MIBK in two stages Single phase co-solvent reaction using THF to produce furfural and LA in two stages Future modifications: Exploration of other catalyst types Single phase co-solvent reaction to produce furfural and 5-HMF in a single stage 33

34 Sigrid Jacobsen Todd Lloyd Matthew Gray Suzanne Stuhler Xia Li Michael Brennan Deidre Willies John Hannon Jonathan Mielenz Jaclyn Qing Qing DeMartini Chaogang Liu Bin Yang Jian Shi Yueh-Du Tsai Jerry Tam Rachna Dhir Rajeev Kumar Yi Jin Heather McKenzie Past and Present Aqueous Phase Biomass Processing Team Taiying Zhang Hongjia Li Michael Studer Simone Brethauer Deepti Tanjore John Bardsley Mirvat Ebrik Nikhil Nagane Charles Cai May-Ling Lu Vanessa Lutzke Samarthya Bhagia Xiadi Gao Jiacheng Shen

35 Questions?