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Catalysis for energy: New challenges for a sustainable energetic development

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Autor: Juan Antonio Melero

Autor: Juan Antonio Melero

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Catalysis for energy: New challenges for a sustainable energetic development Document Transcript

  • 1. Catalysis for energy: New challenges for a sustainable energetic development Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Juan Antonio Melero Hernández Catedrático de Ingeniería Química Departamento de Tecnología Química y Ambiental Grupo de Ingeniería Química y Ambiental Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
  • 2. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Today’s primary energy is coming mainly from fossil fuels Primary Energy coming from fossil fuels (2009): 80 % Transport Energy coming from fossil fuels (2009): ∼ 99 % Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Today’s industrial chemical products are largely based on oil and gas Paint Packaging Fibres Petroleum (90%) Transport Cosmetics Renewables (10%) Pharmaceuticals PRODUCTION OF CHEMICAL PRODUCTS Communication
  • 3. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Release of CO2 Fossil Broken cycle Fuels & Crude oil products Chemical industry Release Photosynthesis of CO2 Biomass Closed Fuels & Biomass cycle products Chemical industry Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sustainable biomass production around the world is enormous (specially, lignocelullosic biomass) • There are a lot of transformation technologies of biomass into fuels and chemicals. BUT … • Currently, most of these technologies are in pilot-plant or even laboratory scale development stage. There are not in commercial stage due to the high-cost of the technology as well as low energy and mass yields as compared with those using fossil resources as raw material.
  • 4. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Integration of biomass conversion processes to yield fuels, power and chemicals. Biofuels LVHV Ethanol Renewable diesel “ Cover Liquid fuels Costs ” CO2 Mass Energy Power Electricity Heat Conversion Feedstocks Processes Chemicals Plastics, resins, foams Agricultural Crops Phenolic resins Agricultural Residues Hydrolysis Solvents Fermentation Chemical intermediates HVLV Forest Residues Adhesives Animal Wastes Bioconversion Fatty Acids “ Profit ” Municipal Wastes Chemical Conversion Paints, Coating Gasification Dyes, Pigments Pyrolysis Detergents Combustion Lubricating Fluids Non-edible Plant and animal oils biomass
  • 5. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Target: Maximize the value derived from the biomass feedstock ¿ Lignocelullosic ? Wastes Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Target: Maximize the value derived from the biomass feedstock
  • 6. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery: “The concept ” An “interesting” first step Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biomass co-processing on refineries
  • 7. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery: “The concept ” Biorefinery Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Lignocellulosic biomass Lignin Cellulose Hemicellulose
  • 8. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Starch-rich biomass (Cereals) Starch Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar rich biomass (sugar beet, sugar cane, …) Sucrose
  • 9. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Triglyceride rich biomass (vegetables oils, fats, …) Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biomass resources Carbohydrates Energy (Sugars) 75 % ¿? Biomass Others Chemicals 5% Oils Fats Proteins Terpenes 20 % Alkaloids Terpenoids Lignin Waxes
  • 10. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues
  • 11. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Syngas platform CHP Cogeneration CO2 Lignocelullosic Biomass Syngas Cleaning Conditioning Tar GASIFICATION T= 850 – 1400 º C Ash P= 1-60 bar Inorganic H2 - CO - CO2 - CH4 Air Syngas O2 Steam Source for the production of biofuels and chemicals Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Syngas platform Alcohol C2+ Acetic Fischer-Tropsch SNG MTBE acid Liquid Fuels Formaldehyde Bio-Olefins (C2-C4) MTO BIOMASS H2 / CO Methanol Bio-Gasoline MTG WGS tic g ly ta min Ca for Fuel Ammonia Re DME Cells H2 Fertilizers
  • 12. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Lignocelullosic 10-20 wt. % Biomass Fast Pyrolysis T= 450 – 550 º C P= 1-5 atm Fast heating Absence of air Short Residence Time 15-25 wt. % Bio-oil 60-75 wt. %
  • 13. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Lignocelullosic Biomass Fast Pyrolysis Fast heating Short Residence Time Bio-oil Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform • Oxygen content: 35-40 wt. % Lignocelullosic Biomass • Low pH ∼ 2.5 • Water content: 10-15 wt. % • Low stability (polymerization) Fast Pyrolysis Fast heating • Low heating value (16-19 MJ/kg) Short Residence Time • Corrosiveness • Poor volatility • Low miscibility with hydrocarbon fuels Bio-oil Need of upgrading
  • 14. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform O2 Hydrodeoxygenation C6H8O4 + 4 H2 C6H8 + 4 H2O Catalytic Cracking Upgrading C6H8O4 C4.5H6 + H2O + 1.5 CO2 BIOMASS Bio-oil Gasification H2 / CO Char Activated Extraction Chemicals Carbon Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues
  • 15. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biogas platform Heat CHP Cogeneration Electricity Biogas Gas distribution Organic Anaerobic network 55-65 CH4 Waste Fermentation 35-45 CO2 Fertilizers Digestate Compost Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues
  • 16. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform : Oil extraction Lignocellulosic Sugar Platform Fraction Syngas Platform Bio-oil Platform Oil seeds (rape, palm, sunflower, soybean) Extraction Vegetable Refining Oil Dedicated oils crops (Jatropha, algae, ..) Protein Cattle Fraction Feed Waste oils (Fried oils, Yellow-grease, …) Refining Crude Oil Non-edible animal fats Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform Biodiesel Transesterification Transport Fuel O O Transport Fuel Glycerol Chemicals Oil Hydrogenation Green-Diesel Proceso Ecofining Transport Fuel Eni/UOP Bio-Gasoline Transport Fuel Catalytic Cracking Bio-olefins Chemicals Chemical / Enzymatic Bio-Surfactants modifications Oleochemical-products
  • 17. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform: Glycerol chemistry O Fermentation HO OH Oxidation HO 1,3-Propanediol OH Hydrogenolysis OH Glycidol HO Sorona Fiber H3C OH Glyceric acid CO2H Propylene glycol Antifreeze OH R2 Humectant Polyester fibers O HO OH HO CH3 O O Glycerol R1 R3 Propanol Mono-, di-, or tri- F glycerate OH OH uels O formulation HO O OH O Diglyceraldehyde Polycarbonates HO O Polyurethanes O O Branched polyesters O and nylons OH Polymerization Glycerol carbonate O A pplications: humectant, plasticizer, fibers, solvent, lubricant, sweetener, bodying agent, antifreeze, and fuel formulation. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefinery concept is built on different “Platforms” Sugar Platform Sugars “Biochemical” Lignocelullosic Residues Fuels Syngas Platform Syngas “Thermochemical” Bio-oil Chemicals BIOMASS Pyrolysis Bio-oil “Thermochemical” Heat Biogas Platform & Biogas Power “Biochemical” Oil crops Platform Oils “Chemical” Lignocelullosic Residues
  • 18. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars extraction Forest Residues Agricultural Residues Lignin (20-25 %) Lignocelullosic Crops Cellulose (35-50 %) C6 (hexoses and pentoses) Lignocelullosic Chemical/Enzymatic Glucose Biomass Hydrolysis Hemicellulose (15-25 %) Simple sugars C5-C6 Straw Corn Stover Bagasse Starch-rich Extraction Starch Hydrolysis Biomass C6 Glucose Sugar-rich Biomass Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars transformation Transportation fuels (hexoses and pentoses) Simple sugars Chemicals
  • 19. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards transportation fuels Anaerobic reaction with enzymes BIOETHANOL Transport Fuel 2 C2H5OH + 2 CO2 DISTILLATION FERMENTATION DDGS Simple sugars DRYING (hexoses) Cattle Feed BIOBUTANOL C6O6H12 Transport Fuel 15 % 96 % 99 % Water content Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards transportation fuels
  • 20. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Lignin valorization Syngas Platform Transport Fuel Bio-oil Platform Heat & Electricity (CHP) Chemical Added value chemicals Lignin Transformations Current Catalytic hydrogenation Technology Petroleum Industry Catalytic oxidation More complex molecules J. Zakzeski. “The catalytic valorization of lignin for the production of renewable chemicals” Chem. Rev. 2010 , 110, 3552-3599 Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards chemicals Added value bio-chemicals Platform molecules (or building block chemicals) are molecules with multiple functional groups that possess the potential to be transformed into new families of useful molecules. Bio-transformations Chemical Transformation Sugars Glucose Fructose Xylose Arabinose Lactose
  • 21. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards chemicals The Office of the Biomass program, US has recently identified 12 building blocks that can be produced from sugars via biological or chemical conversions Building Blocks C3 Glycerol 3 hydroxypropionic acid C4 1,4 succinic acid 1,4 fumaric acid 1,4 malic acids Aspartic acid 3-hydroxybutyrolactone C5 Levulinic acid Glutamic acid Itacomic acid Xylitol/Arabinitol C6 Sorbitol Glucaric acid 2,5 furan dicarboxylic acid Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? OH Glycerol HO OH Chemical – Transesterification of oils Chemical routes Hydrogenolysis Oxidation Dehydration Polymerization Etherification
  • 22. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 3- Hydroxypropionic acid Bio-transformations – Fermentation of sugars Chemical routes Hydrogenation Dehydration Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 1-4- Four carbon diacids (Succinic, Fumaric and Malic) Bio-transformations – Fermentation of sugars Chemical routes Hydrogenation Aminations Polymerizations
  • 23. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Aspartic acid Bio-transformations – Fermentation and enzymatic conversion of sugars Chemical – Amination of fumaric acid Chemical routes Hydrogenation Dehydrations Polymerizations Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 3-Hydroxybutyrolactone Chemical – Oxidative degradation of starch (H2O2) Chemical routes Hydrogenation Polymerizations
  • 24. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Levunilic acid Chemical – Catalytic dehydration of sugars (C6) Chemical routes Hydrogenation Oxidations Condensations Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Glutamic acid Bio-transformations – Fermentation of sugars Chemical routes Hydrogenation
  • 25. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Itaconic acid Bio-transformations – Fermentation of sugars Chemical routes Hydrogenation Polymerization Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Xylitol Chemical – Hydrogenation of xylose (C5) Chemical routes Hydrogenolysis Oxidation Polymerization
  • 26. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Sorbitol Chemical – Hydrogenation of glucose (C6) Chemical routes Hydrogenolysis Oxidation Polymerization Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Glucaric acid Chemical – Oxidation of starch with nitric acid Chemical routes Dehydration Polymerization
  • 27. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 2,5- Furan dicarboxylic acid (FDCA) Chemical – Oxidative dehydration of C6 sugars Chemical routes Hydrogenation Polymerizations Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards chemicals Most of them are new processes Most of them are known processes Most of them are not commercial Commercial use Bio- Chemical- Chemical- Platform Added value Sugars Molecules Transformations bio-chemicals Transformations Challenges Challenges Low cost fermentation routes New heterogeneous catalysts to replace homogenous. New processes New building blocks New catalysts robust towards biomass impurities Use of oxidant of low cost (air, oxygen , …)
  • 28. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefineries: Future outlook Fuels ¿? Fossil Biomass Sources Chemicals CmHn Heat & Yes CmHnOx Power But … Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefineries: Future outlook New catalysts for New processes for the hydrolysis of this new feedstock lignocelullosic feedstock (more efficient, Development of low cost safe and environmentally friendly) bio-transformation processes (fermentation and enzymatic) Scaling-up of the processes Challenges & Opportunities Technologies integration Biomass valorization can use New feedstock New processes commercial technology developed and products for petroleum refining nd petrochemicals Short- Medium- term solution
  • 29. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefineries: Future outlook 2nd Generation Biorefinery 1st Generation Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • References J. J. Bozell, G. R. Petersen. Technology development for the production of bio-based products from biorefinery carbohydrates – the US Department of Energy´s “Top 10” revisited. Green Chemistry 12 (2010) 539-554. J. Zakzeski, P. C. A. Bruijinincx, A. L. Jongerius, B. M. Weckhuysen. The catalytic valorization of lignin for the production of renewable chemicals. Chemical Review 110 (2010) 3552-3599. M. F. Demirbas. Biorefineries for biofuel upgrading: A critical review. Applied Energy 86 (2009) 151-161. A. Demirbas. Biorefineries: Current activities and future developments. Energy Conversion and Management 50 (2009) 2782-2801. S. Fernando, S. Adhikari, C. Chandrapal, N. Murali. Biorefineries: Current status, challenges and future direction. Energy & Fuels 20 (2006) 1727-1737.
  • 30. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • References Catalysis for energy: New challenges for a sustainable energetic development Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Juan Antonio Melero Hernández Catedrático de Ingeniería Química Departamento de Tecnología Química y Ambiental Grupo de Ingeniería Química y Ambiental