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The Biorefinery Concept: Its emergence and application on Long Island

The Biorefinery Concept: Its emergence and application on Long Island. Devinder Mahajan Advanced Energy Research and Technology Center (AERTC)/ Chemical & Molecular Engineering (CME) Stony Brook University & Energy Sciences and Technology Department (ESTD) Brookhaven National Laboratory

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The Biorefinery Concept: Its emergence and application on Long Island

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  1. The Biorefinery Concept: Its emergence and application on Long Island Devinder Mahajan Advanced Energy Research and Technology Center (AERTC)/ Chemical & Molecular Engineering (CME) Stony Brook University & Energy Sciences and Technology Department (ESTD) Brookhaven National Laboratory Presented at: “Energy Long Island Conference 2007- Challenges of Today and Tomorrow” Farmingdale State College Farmingdale, NY October 25-26, 2007

  2. The Future Fuels Group (BNL/SBU) • Collaborators • CR Krishna (BNL) • T. Butcher (BNL) • N. van der Lelie (BNL) • K. Ro (USDA) • P. Hunt (USDA) • M. Rafailovich (SBU) • H. Zhang (SBU) • M. Castaldi (Columbia U.) • Farmingdale • H. Tawfik • 10+ Students • Students • Graduate • - M. Eaton • M. Anjom • P. Kerkar • Y. Hung • CME Undergrads • SULI/Battelle Fellowship program • 9+ students • FUNDING • U.S. Department of Energy (US DOE) • BNL: Laboratory Directed R & D (LDRD) • U.S. Department of Agriculture (USDA) • USB: Research Foundation • Industry

  3. Alternate Energy Options Non-petroleum options ◊ Biomass* ◊ Geothermal* ◊ Solar ◊ Wind ◊Tidal Impact Sectors ◊ Transportation ◊Utilities (electric, gas) ◊Manufacturing * Focus of R&D in our group

  4. Presentation Focus ◊ “Biorefinery” concept and “Distributive fuel production” concept ◊ Biofuels ◊Our Research in biofuels ◊ Relevance to Long Island

  5. Possible Routes from Biomass to Energy Fuels • Source: 1 billion tons of biomass available (USDA estimate). • Biomass Processing- • Sugar Platform – “Biochemical Route” • Syngas Platform- “Thermochemical Route” gy Resources Conversion Product Market Solid Biomass (Wood, straw) Combustion Heat Heat/CHP Gasification Fuel Gas Electricity Wet Biomass (organic waste, manure) Pyrolysis Bio oil Transportation Fuels Sugar, Starch plants (sugar beet, cereals) Digestion Biogas Hydrolysis & Fermentation Bioethanol Chemicals Oil Crops (rapeseed, other oils) Extraction & Esterification Biodiesel Source: Chemical Engineering, October 2006

  6. Biorefinery Concept Esterification Biodiesel Biomass Fermentation Bioethanol Gasification Syngas BioFuels* * Biofuels includes any liquid fuel ◊Biorefinery concept is appealing because it will use the existing infrastructure. ◊Biomass to BioFuels- Next-generation technologies are needed. Fischer-Tropsch technologies will play a role.

  7. Biofuels Definition: Fuels derived from CO2-net neutral feedstocks. Gasoline Consumption (2005): 140 billion gallons Biofuels Market Share (2005): 4% gasoline consumption Target Fuel200520122025 (gallons/year) Bioethanol [U.S.]* 5x109 7.5x10960x109 Biodiesel [U.S.]** 0.6x109 1.3x109 (2008) --- Bioethanol [Brazil]** 4.5x109 *Corn based; **Data from NBB; ***Sugarcane based(45% of the world total). Goal: Replace 75% oil imports by 2025.

  8. Biofuel 1: Biomass to Biodiesel Biomass Esterification Biodiesel • Biodiesel Production Methods • Base catalyzed transesterification of oil • Direct acid catalyzed transesterification of oil • Convert oils into fatty acids and then to biodiesel

  9. Biomass to Biodiesel- Production Base catalyzed esterification reaction CH2OCOR''‘ CH2OH R'''COOR CHOCOR'' + 3 ROH Catalyst CHOH + R''COOR CH2OCOR‘ CH2OH R'COOR (100 lbs) (10 lbs) (10 lbs) (100 lbs) Oil or Fat Alcohol (excess) GlycerinBiodiesel (Triglyceride) Mono-alkyl ester Oil or Fat: Soybean, Palmitic, oleic, stearic, linoleic acids Catalyst: KOH, NaOH ROH: MeOH, EtOH • The process needs MeOH or EtOH • Glycerin as a byproduct is a major issue.

  10. Biomass to Biodiesel- Process Base Catalyzed Esterification of Oils Source: Lurgi Process • Advantages • Low T • Low P • Direct high conversion (~ 98%)

  11. Biodiesel: Properties • ASTM Standard- D6751 • Reaction completion • Glycerin removal • Catalyst removal • Free fatty acids removal • Fuel properties of biodiesel from Soybean oil ΔHg = gross heat of combustion; Tflash = flash point (Penske Martins closed cup); CP = cloud point; PP = pour point

  12. Biodiesel: Fuel Quality for Diesel Engines • ASTM Specification for B100 for Blending has been developed (D6751) • Changes being considered to improve quality • Attempts are being made to address stability and compatibility • with newer diesel technology concerns of engine manufacturers • Additional research required to define and test for stability • Lack of data relating stability and deposit formation in engine

  13. Biodiesel Production- Economics • Improve Esterification • - Processing steps • Fuel to diesel engine specifications • - Minimize impurities • Glycerin Utilization • - Catalytic conversion to fuels • CH2OH • CHOH CO + H2 • CH2OH Pt Fuels 250- 3000C ◊ Work is ongoing at BNL/SBU to find a catalyst for conversion of this byproduct to fuels.

  14. Biofuel 2: Biomass to Bioethanol Biomass Fermentation Bioethanol • C6H12O6 (aq) 2 C2H5OH (aq) + 2 CO2 (g) • Glucose • Theoretical C Utilization: 67% • CO2: product of fermentation process • Typical processing time: 48 hrs Yeast

  15. Grain (Starch) Milling Hydrolysis Saccharification Water Centrifuge Evaporation Distillation Fermentation Drying Dehydration Syrup CO2 DDG Ethanol Bioethanol Production- Schematics

  16. Alcohol Recovery Thermo-Stable Alpha Amylase Milo Corn Wheat Rye Barley Tapioca Glucoamylase Yeast Distillation & Dehydration Liquefaction Saccharification Fermentation Water JET COOKER >100° C 5–8 MIN * STORAGE TANK 60° C 8–10 HRS (optional) GRINDING SLURRY TANK * SECONDARY LIQUEFACTION 95° C ~90 MIN DDGS Bioethanol Production- Plant Source: Waste Conversion Technologies, UCLA

  17. Our Research on Biofuels- Next-generation Technologies (DOE Report) Goal: Maximize C conversion

  18. Distributive Fuel Generation Concept- BioFuels on a Farm • Goal • Skid-mounted fuel production plants- Economy of scale! • Approach** • Biomass contains both C and H atoms- Total carbon utility is • the key. • - driven by highly active catalysts • - driven by process modifications ** The approach combines process requirements with process chemistry to design next-generation atom economical fuel production technology.

  19. Atom Economical Synthesis of Liquid Fuels CO2 Ultra-Clean Fuels Biomass By-products Process Waste

  20. Biomass: Structural Units Source: US DOE Cellulose: Polymer and cross-linkages among glucose units. Hemicellulose: 5, 6 carbon sugars, sugar acids, acetyl esters- more complicated than cellulose. Typical composition Carbohydrates/Sugars: 75% Lignin: 25% Lignin: Phenolic polymers- impart strength to plants.

  21. Biofuels via Catalytic Thermal Processing-An Alternative to the Bio Route Biomass Gasification Syngas BioFuels • Technical Barriers (U.S. DOE) • Handling varying feed composition • Syngas clean-up steps needed • Develop utilization of produced gas • [Quote from T. Patzek, UC Berkeley- Presented at the National Press Club Conference, Washington, DC, August 2005] • “Thermodynamically and kinetically, lignocellulosic ethanol is the poorest choice in comparison with: 1) direct Biomass burning for Electricity or 2) Biomass Gasification”.

  22. Biofuels from Biomass- The Gasification Route Methanol B I O M A S S (Feedstock) Hydrogen SYNGAS CO,CO2,H2 (direct & Indirect) F-T Liquids (Biorefinery Concept) Alcohols (C2+) CO + 2 H2 CH3OH CO + 2 H2 -(CH2-)n + H2O

  23. Syngas Catalysis: Reaction Characteristics CO + H2 Fuels** H = (-) (Oxygenates, Hydrocarbons) • Reaction Characteristics • Exothermic • Require a Catalyst • Commercial catalyst: micron-sized • Gas/solid reaction in packed-bed reactor • - Poor heat management • Poor product selectivity • Fuels are Ultra-Clean

  24. Syngas Catalysis: Process Engineering Materials Science/Chemistry/Chemical Engineering Goal: Atom Economy Approach:Liquid Phase Low Temperature (LPLT) Approach Controlled-site Catalyst** Liquid Phase Operation Low Temperature M **Use Single site or Clusters M M M ◊Center for Functional Nanomaterials (CFN) and Process Engineering Laboratories in the new AERTC building will be utilized for this work.

  25. BioMethanol Synthesis from Biomass • Why Methanol? • A liquid energy carrier- compatible with existing infrastructure. • Excellent feedstock for fuels and chemicals (Replacement for • petroleum feedstock). • Contains 12.5 wt% H2 - MeOH reacts with H2O to extract more H2 • (total H2: 18.75 wt%), highest H2 storage capacity. • Methanol is a transition to “HYDROGEN ECONOMY” • Methanol is converted to ethanol through “Homologation” (C-C Coupling) • Challenge • Develop an efficient Biomethanol synthesis process from Biomass.

  26. Flow Diagram: Commercial Methanol Synthesis • Catalyst is micron-sized Cu/ZnO • Uses fixed bed or slurry-phase • Problem identified: • < 20% syngas (C) conversion per pass. Requires large gas recycle, expensive compressors.

  27. An Ideal Methanol Process T and P Curves for Methanol Synthesis (Lit.)

  28. Evolution of “Single-site” MeOH Catalyst • External activation of CO by Alkoxide base • Hydrogenation of activated CO by Ni Pt-Group Metals AM-OR Solvent KOMe/NiCl2/Triglyme-MeOH CO/H2 MeOH

  29. Methanol Synthesis: Process Comparison Parameter (Bio) “LPLT”* Commercial Syngas production ……… Air O2 separation plant Reaction T, oC …………….. 110 265 Reaction P, MPa ………… 1 5 Equilibrium CO Conversion,% 94 61 Operating CO Conversion,% 90 20 Gas recycle, No High *NRC Report (1992)- Catalysis Looks to the Future”

  30. H2 Anode H3O+ Electrode H2O T < 150ºC O2 Cathode + T < 140ºC T < 100ºC H2O Air End use Application of Biofuels- Low Temperature Cascade for Fuel Cell Biomethanol Synthesis Biomethanol Decomposition Fuel Cell Water-Gas Shift 3H2 + CO2 T < 150ºC CO + 2H2 + H2O Biomass Methane CH3OH + H2O  CO2 + 3H2  H2 Storage capacity: 18.75 wt.%

  31. The Future of BioFuels • Interest from Major Commercial Companies • Dupont • Chevron • BP • VeraSun • Broin • Other Biofuels – Biobutanol • Advantages (compared to Ethanol) • Higher energy content • Easily blends with gasoline • Higher blending ratio • Oxidation products less volatile (???) • Butanol yields butraldehyde/butyric acid • Ethanol yields acetaldehyde/acetic acid • Processing Cellulosic Materials • Breakdown complex molecules to simple sugar for further processing to biofuels. • Develop better bio or chem. Catalysts • - DuPont/NREL (Zymomonas mobilis). • Utilize Glycerin from Biodiesel Production

  32. The Future of BioFuels • Other biofuels portfolio • Biobutanol, biomethanol, biohydrocarbons (F-T process) • Tax Credits(Energy Policy Act of 2005) • 10 ¢/ gallon (up to 15x106 gallons of agri-biodiesel. • Net energy content (based on LCA)* • Energy input: 1.00 • Biodiesel (1.93) > bioethanol (1.25) • Environmental Concerns • Increased use of 1) fertilizers and 2) Pesticides. • Fate of environmental oxidation products • *Proc. Natl. Acad. Sci. USA 103 11206 (2006).

  33. A Path to Sustainable Development • Resource consideration - 1 billion ton biomass is available • Distributive fuel production - “Small is beautiful” • Process and related chemistry need to be integrated for Product flexibility • Closely related process chemistry •  “Alcohol Economy”- A transition to “Hydrogen Economy”

  34. Relevance and Challenges to Long Island • What are our resources? - MSW, trapped grease (Bergen Point), wood chips, pine cones • Environmental Considerations - Protect Pine Barrens and Aquifers • Small plants could be located on LI (work with towns, Counties) •  Nurture intellectual resource of New York State- Develop and license technologies globally

  35. Publications Guest Editor: D. Mahajan Clean Fuels Methane Hydrates 2007 Biomass to Fuels Scheduled publication Dec. 2007 2005

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