Top Global Challenges. GT Chem 2312 Students ENERGY WATER FOOD CHEM 2312 ENVIRONMENT TERRORISM & WAR

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1 BioFueling The Future Challenges pportunities GT Art J. Ragauskas Georgia Institute of Technology School of Chemistry and Biochemistry

2 Top Global Challenges GT Chem 2312 Students ENERGY WATER FD CHEM 2312 ENVIRNMENT TERRRISM & WAR

3 Research pportunities: New Industrial Economy David Morris - early 1980s Coined the term "carbohydrate economy" Envisaged shifting society's engine toward renewable, environmentally benign materials from agro/forestry-based materials - Agricultural Risk Protection Act of 2000 Title III: Biomass R&D Act of 2000, established the Biomass Research & Development Board. Dr. Arden L. Bement, Jr. Director, National Science Foundation

4 Defining a Biobased Economy An economy based on renewable raw materials to produce products and energy in a sustainable manner

5 Biofuels Future Biomass Resources Today Saccharification H Fermenation Ethanol Future Biomass Deconstruction Catalyst or Enzymes H H H H Fermentation H 3 C H 2 C H H

6 Biofuels Future - Biomass Resources Pine Switchgrass Poplar Sycamore Sweetgum Sorghum Black Locust Miscanthus Lower Cost No Competition with Food Demand Higher Availability

7 Biofuels Future Integrated Biorefinery The integrated biorefinery is facility that fully integrates biomass production and conversion 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 ak 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),

8 Biofuels Research Challenges: Plant Science 5-year old tree Research bjective More, Bigger, Better; the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production Georgia GA Tech Challenges Can we Tailor Georgia s Wood Resources for Biofuels Reduced lignin Increased carbohydrates Faster growing Loblolly Pine Poplar/Hardwoods Improved Switchgrass GA Tech School of Biology/Forest Biology/Systems Biology School of Chemistry/Biochemistry Society Issues: If we build it Will they come?

9 Biofuels Research Challenges: Separations Extraction of Value Added Chemical Neutraceuticals Bioactive agents H Pine Sitostanol System Solutions Need Integrated Research Teams Wang et al. Argonne 1999 Value Added Materials Nanocellulose/hemicellulose Lignin for carbon fibers BioFuels Ethanol Dimethyl ether Biodiesel Biogasoline DE

10 BioFuels Research Challenges Conversion Bioethanol <<<< Sugars <<<< Hemi/Cellulose << Biomass Efficient Depolymerization of Cellulose Biomass Pretreatments Conventional Solvents New Solvents Deconstruction Enzymes Improved hydrolysis active In-situ Expression cellusomes Fundamental biomass chemistry Societal Issue: Leadership-Education

11 Biofuel - Bioethanol

12 Biofuel Research Challenges

13 Biofuels Research - ngoing Studies verview of Processing Biomass to Bioethanol H H H Biomass Biomass Pretreatment Hydrolyzed Biomass Fermentation of Hydrolyzed Biomass Bioethanol + Residue Loblolly Pine H H Hybrid Popular Switchgrass Miscanthus giganteus The efficient processing of lignocellulosics into biofuels is contingent on the characterization of the chemical constituents of plant carbohydrates and lignin and their changes in structure throughout the process. Several key parameters need to be addressed to facilitate practical bioconversion of non-food agricultural/woody biomass into ethanol including: Amounts and degree of cellulose crystallinity Amounts and structure of hemicelluloses, lignin, and low-molecular extractives Inorganic elements

14 Early Adoption Paper Mill Sludge- Virgin/Recycled - negative value stream Recycled Paper

15 Biofuels: Enzymatic Hydrolysis of Cellulosics Cellulose: I α is more abundant in lower plants/bacteria I β is more abundant in higher plants Analysis of Cellulose Crystallinity: X-ray, NMR, FT-IR 4 6 CH 2 H H 1 4 CH 2 H H 1 C-2, 3, 5 C-1 C-4 C-6 Question: What role, if any, does cellulose ultra structure have on enzymatic hydrolysis?

16 Biofuels: Enzymatic Hydrolysis of Cellulosics Cellulase from Trichoderma reesei cellobiohyrolases endoglucanases β-glucosidases NREL Cellulolytic filamentous fungus Relative intensity, % Cellulose: Ια I α Cellulose: I α Pulp Hydrolysis time, hr Glucose yield, % avicel Relative intensity, % Ιβ Cellulose: I β Hydrolysis Time, h Hydrolysis time, hr

17 Biofuels: Enzymatic Hydrolysis of Cellulosics Relative intensity, % Post-hydrolysis percentage, % Para-crystalline Hydrolysis time, hr avicel pulp Hydrolysis Time, h Relative intensity, % Amorphous Hydrolysis time, hr First study quantifying change in para-crystalline phase First to quantify changes in ultrastructure of kraft cellulose after cellulase treatment Complements recent study by Hayashi on cellulase changes to I α :I β from Cladophora microcryst. cellulose

18 Today- Tomorrow s Forest Products BioRefiner Value-Added Chemicals Bark Energy Biofuels Wood Debarking Collection Wood Chipping Proposed Hemicellulose Extraction Stage Wood Chips Wood Extractives Chemical Markets Wood Hemicellulose Sugars Extracted Woodchips Pulping Combustion of Chemical Pulp Waste Energy Pulping Chemicals Bioethanol Fermentation Pulp Bleaching Unbleached Pulp Papermaking Papermaking Current Products: Pulp, Tall il, Turpentine Future Select Hemicellulose, Wood Extractives

19 BioRefinery: Hemicellulose Extraction verview of Experimental Plan Southern Loblolly Pine Chips Wood Chip Pre-extraction Acidic Basic Control Kraft Pulping Wood Chips Kraft Pulping Hemi-Extracts Pulp Yield Fiber Properties Paper Properties Pulp Yield Fiber Properties Sheet Properties Hemi Yield Lignin Yield Hemi Composition

20 BioRefinery: Hemicellulose Extraction Acidic Pre-Extracted Woodchips: Pretreatment Modification Prior Studies Direct H 2 S 4 /H 2 Alternative Approach Delayed H 2 S 4 /H 2 t= h Spray Chips t=0 1 h, 150 o C

21 Novel xidative Chemistry In Ionic Liquids for Lignin CH 3 H H C 800 C 900 CH 3 H3C CH3 CH 3 H CH3 C CH3 CH 3 H H 8 C 22 Biodiesel Biochemicals Biomaterials H3C CH 3 H H CH3 CH 3 H xid. CH 3 CH3 CH3 CH3 Need New Fundamental Green Chemistry Studies Catalytic xidative System (s) Preferably in Ionic Liquid Inert solvent Tailor solubility of lignin Almost no vapor pressure Facilitate isolation of oxidized fragments CH 3 CH 3 Classical Ionic Liquids Cations Salts Anions R R 1 R 2 N N N + + Imidazolium Pyridinium R 2 R 2 PF 6 BF 4 CF 3 S 3 (CF 3 S 3 ) 2 N R 3 N + R 1 R 3 P + R 1 MeS 3 R R AlCl 4 Ammonium Phosphonium Cl(Br)

22 BioFuels Research Challenges Conversion Biomass Biomaterials Biochemicals (Waste) Biofuels (Waste) Pyrolysis Gasification Research Needs Gas cleanup/tars New catalyst Biological Fisher Tropsch routes Syn Gas Biofuels Biochemicals Power Heat Electricity

23 BioFuels Path Forward GT Strengths Georgia Institute of Technology Strategic Energy Institute SEI mission is to actively engage in and facilitate energy technology development, assessments, demonstration projects and policy guidance based on scientific facts, engineering principles and economic realities. Several Programs Woody Cellulose for Ethanol Transportation Fuel in Georgia Energy Security Rural Development GA Advantage Performance/Policy GA SW/HW GA Tech Distribution Today s Technological Needs Conversion Tomorrow s Technological Breakthroughs

24 Acknowledgements Acknowledgements NSF, USDA GT FRP Biomass to Biofuels, Biopower, Biomaterials

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