BioFuels Research Opportunities/Needs Georgia Institute of Technology School of Chemistry and Biochemistry Art J. Ragauskas
Brief Biofuels: History Biodiesel Bioethanol 1908 Henry Ford’s Model T was 1898 Rudolph Diesel powered by ethanol generated demonstrated his compression from bioethanol plants he owned ignition engine at the World's in the midwest was partnered Exhibition in Paris with peanut with Standard Oil oil 300 Giant Oil Field Discovery G. W. Bush 2006 State of Union 250 Billion BBls/Decade Address “America is addicted to oil, 200 which is often imported from unstable parts of the world. The best way to 150 break this addiction is through Million BBls/day 100 technology…” . 50 0 19001910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2005 2010
Brief Biofuels: Perspective Energy/Transportation Fuels Costs Options Benefits Modern Lifestyle Economy Environment
Brief Biofuels: Perspective US: Currently Bioethanol 2% Biodiesel 0.01% Total Renewable Fuels Consumption for Transportation Three Total Renewable Fuels Consumption for Transportation Three Cases, 2003-2020 (Billion Gallons/Year) Cases, 2003-2020 (Billion Gallons/Year) 7000 6 6 RFS Schedule RFS Schedule U.S.A. Bioethanol 6000 5 5 S.517 S.517 MM Gal. Annual Cellulose Ethanol Credit Cellulose Ethanol Credit 5000 4 4 4000 3 3 Reference Reference 5 additional Northeast 5 additional Northeast 3000 2 2 States Ban MTBE States Ban MTBE 87% Reduction in MTBE 87% Reduction in MTBE 14 States Ban MTBE 14 States Ban MTBE Starting in 2004 Starting in 2004 1 1 2000 0 0 1000 2003 2003 2006 2012 2020 2006 2012 2020 0 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2012 BioFuel Resources Methyl tert-butyl ether (MTBE) • USA - Corn Additive in unleaded gasoline. • Brazil – Sugar Cane • Europe – Sugar beet, Potato Rapeseed/sunflower
Biofuels Future Biomass Resources OH OH Today Today Amylase Amylase Yeast Yeast O O H 2 H 2 HO HO C C HO HO OH OH H 3 C H 3 C OH OH OH OH Acid Fermentation OH Catalyst O H 2 HO Future Biomass C HO or OH H 3 C OH O OH Enzymes HO HO OH OH
Biofuels Future Biomass Resources OH OH O OH O OH O HO O HO O HO O HO O OH O OH O OH OCH 3 OH HO OH Cellulose Cellulose HO OH HO Polymer of Polymer of O OCH 3 β -(1,4)-glucan β -(1,4)-glucan H 3 CO Degree of Polymerization Degree of Polymerization HO O O OCH 3 HO ~300 – 15,000 ~300 – 15,000 HO OCH 3 OH OH HO O OAc O OAc O O O O OH HO HO AcO OCH 3 O HO O AcO O-Xylan HO HO OH OH HO O O HO O OH OH HO O OAc O O OAc O O O O O HO Production:~ 35 – 50% Production:~ 35 – 50% O HO O OCH 3 HO O Production: ~ 15 – 30% Production: ~ 15 – 30% % % O O OCH 3 Major Major OH 0 0 Hemi Hemi HO O OH HO OH O 3 3 OH OH - - Global Global Cellulose Cellulose 0 0 OH 2 2 Lignin Lignin Biopolymers Biopolymers ~ ~ HO HO H 3 CO O : : n n O HO O O OCH 3 o o Short chain Short chain O HO i i t t H 3 CO OCH 3 c c Polymer Polymer OH OH u u HO HO branched,substituted branched,substituted d d OH OH Derived from Derived from o o O r r polymer of pentoses polymer of pentoses HO P P OCH 3 and hexoses and hexoses OH OH OH OH OH OH HO OH OH OH OH OH OH OH OH O OCH 3 OH OH O O O O O O O HO HO HO HO HO HO OH OH HO HO OH OH HO HO OH OH OH OH OH OH OCH 3 OCH 3 OCH 3 H 3 CO H 3 CO OCH 3 OCH 3 OH OH O O OH OH O O O OH OH OH OH HO HO HO HO OH OH HO HO OH OH OH OH Degree of Polymerization ~70 - 200 Degree of Polymerization ~70 - 200 OH OH Lower Cost Higher Availability No Competition with Food Demand
Biofuels Future Biomass Resources Cellulose Cellulose Polymer of Polymer of β -(1,4)-glucan β -(1,4)-glucan DP: ~300 – 15,000 DP: ~300 – 15,000 Content: ~ 35 – 50% Content: ~ 35 – 50% Content: ~ 15 – 30% Content: ~ 15 – 30% Major Global Major Global Content: ~ 20 - 30% Content: ~ 20 - 30% Biopolymers Biopolymers Hemi Hemi Lignin Lignin Cellulose Cellulose Polymer Polymer Short chain Short chain Derived from Derived from branched,substituted branched,substituted Coniferyl, Coumaryl, Coniferyl, Coumaryl, polymer of sugars polymer of sugars Sinapyl, Alcohol Sinapyl, Alcohol DP: ~ 70 - 200 DP: ~ 70 - 200 % ∼ Lignin BioResource Hemicellulose Cellulose Softwood 27 28 39 Hardwood 25 30 40 Corn Stover 18 22 38 Wheat Straw 23 21 38 Fine Paper - 20 80 Switch Grass 18 21 31 Need to utilize all Bioresources BioPolymers
Biofuels Future Integrated Biorefinery The biorefinery is facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. It fully utilizes all components of biomass to make a range of foods, fuels, chemicals, feeds, materials, heat and power in proportions that maximizes sustainable economic development. Imperial College Georgia Institute Oak Ridge National London of Technology Laboratory The Path Forward for Biofuels and Biomaterials. Ragauskas, A.J.; Williams, C.K.; Davison, B.H.; Britovsek, G.; Cairney, J.; Eckert, C.A.; Frederick, W.J., Jr.; Hallett, J.P.; Leak, D.J.; Liotta, C. L.; Mielenz, J.R.; Murphy, R.; Templer, R.; Tschaplinski, T. Science (2006), 311(5760), 484-489
Biofuels Research Challenges: Plant Science Research Objective “More, Bigger, Better;” the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production • ~ 8 dry Mg Ha-1 yr-1 for willow in Sweden to 10-22 dry metric tons per hectare yr-1 in U.S. for short-rotation woody crops, commercial plantations in Brazil up yo 20 dry Mg ha-1 yr-1. • Manipulating photosynthesis genes to increase the initial capture of light energy • Manipulation of genes involved in nitrogen metabolism • Overexpressing a Glutamine Synthase (GS1) gene transgenic poplar, tree height increased to 41% greater than control plants • Repressing a single lignin biosynthetic gene, 4 CL, resulted in a reduction in lignin content with a concomitant increase in cellulose
Biofuels Research Challenges: Plant Science Research Objective “More, Bigger, Better;” the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production • Lignin biosynthetic gene CCR is downregulated in poplar, the cellulose component of the plant cell wall is more easily digested by the bacterium Clostridium cellulolyticum, and twice as much sugar is released • Enhanced plant oils, waxes, naval stores • Endogenous production of polysaccharide hydrolyase enzymes could also be coupled with enhanced plant biomass production made possible by recent advances in molecular farming > Soil productivity/management > Collection systems
BioFuels Research Challenges Conversion Bioethanol <<<< Glucose <<<< Cellulose << Biomass Efficient Depolymerization of Cellulose – Glucose • Biomass Pretreatments – Conventional, Organic Solvents, Steam Explosion – Ionic Liquids, Nearcritical Water, Gas Expanded Liquids • Acid Catalyzed Hydrolysis of Cellulose – Catalysis – Conditions – Reduction/elimination of fermentation inhibition by- products
Biofuels Research Challenges:Biomass Characterization Advanced Spectroscopic Increased photosynthesis Optimized photoperiod response Bio-Analysis – High Volume Optimized crown/leaf architecture Pest/disease resistance, Enhanced biomass production/ Drought/cold tolerance acre by reducing perception of Floral sterility nearest neighbor by manipulating photomorphogenic responses of Regulated dormancy phytochrome Red/FR light perception system Delayed leaf senescence Computational Greater carbon allocation to stem diameter vs. height growth Less extensive root system to Data Analysis maximize aboveground biomass Controlled and readily processable cellulose, Optimal nitrogen acquisition and use hemicellulose, and lignin. Tailored biomass composition with value-added chemicals Need for Rapid, Inexpensive Detailed Topochemical Characterization of Biomass Initial/Processed • Cellulose – Structure, DP, Ultrastructure, Location • Hemicelluloses – Chemical constituents, Structure, DP, Location • Lignin - Chemical constituents, Structure, DP, Location • Extractives - Structure OCH OCH 3 OCH OCH 3 3 3 DMSO DMSO DMSO DMSO 800 1000 1200 1400 1600 1800 2000 m/z 0.50 φ - φ - φ φ -OH -OH OH OH 0.4 φ φ φ φ 0.3 A 0.2 ROR ROR ROR ROR 0.1 φ - φ - φ φ C=O C=O C=O C=O φ φ -CH -CH CH 2 CH 2 - φ - φ 2 - 2 - 0.00 1100.0 1500 2000 2500.0 NM
Biofuels Research Challenges: Separations Extraction of Value Added Chemical • Neutraceuticals • Drugs H • Bioactive agents Pine Sitostanol HO Value Added Materials • Nanocellulose/hemicellulose • Lignin for carbon fibers • Chemicals/Polymers BioFuels • Ethanol DOE • Butanol • Dimethyl ether • Biodiesel Wang et al. • Biogasoline Argonne 1999
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