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Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
Catalysis for energy: New challenges for a sustainable energetic development
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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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  • 1. Grupo de Ingeniería Química y Ambiental Catalysis for energy: New challenges for a sustainable energetic development Juan Antonio Melero Hernández Catedrático de Ingeniería Química Departamento de Tecnología Química y Ambiental Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 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 Cosmetics Pharmaceuticals Transport Communication Petroleum (90%) Renewables (10%) PRODUCTION OF CHEMICAL PRODUCTS
  • 3. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? Fossil Broken cycle Release of CO2 Chemical industry Crude oil Fuels & products Biomass Closed cycle Photosynthesis Biomass Release of CO2 Chemical industry Fuels & products 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. Feedstocks Conversion Processes Biofuels Ethanol Renewable diesel Liquid fuels Power Electricity Heat Chemicals Plastics, resins, foams Phenolic resins Solvents Chemical intermediates Adhesives Fatty Acids Paints, Coating Dyes, Pigments Detergents Lubricating Fluids Plant and animal oils Agricultural Crops Agricultural Residues Forest Residues Animal Wastes Municipal Wastes Non-edible biomass Hydrolysis Fermentation Bioconversion Chemical Conversion Gasification Pyrolysis Combustion CO2 Mass Energy HVLV “ Profit ” LVHV “ Cover Costs ”
  • 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 Biomass Carbohydrates (Sugars) 75 % 20 % Lignin Others 5 % Oils Fats Proteins Terpenes Alkaloids Terpenoids Waxes Energy Chemicals ¿?
  • 10. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms” Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms”
  • 11. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Syngas platform Lignocelullosic Biomass GASIFICATION H2 - CO - CO2 - CH4 Syngas Source for the production of biofuels and chemicals T= 850 – 1400 º C P= 1-60 bar Air O2 Steam Syngas Cleaning Conditioning CO2 Tar Ash Inorganic CHP Cogeneration Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Syngas platform H2 / CO WGS H2 Methanol Catalytic Reform ing DME Fuel Cells Bio-Gasoline MTG MTBE Fischer-Tropsch Liquid Fuels SNG Bio-Olefins (C2-C4) MTO Acetic acid Formaldehyde Ammonia Fertilizers BIOMASS Alcohol C2+
  • 12. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms” Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Lignocelullosic Biomass Fast Pyrolysis Bio-oil Fast heating Short Residence Time T= 450 – 550 º C P= 1-5 atm Absence of air 60-75 wt. % 15-25 wt. % 10-20 wt. %
  • 13. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Lignocelullosic Biomass Fast Pyrolysis Bio-oil Fast heating Short Residence Time Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Lignocelullosic Biomass Fast Pyrolysis Bio-oil Fast heating Short Residence Time • Oxygen content: 35-40 wt. % • Low pH ∼ 2.5 • Water content: 10-15 wt. % • Low stability (polymerization) • Low heating value (16-19 MJ/kg) • Corrosiveness • Poor volatility • Low miscibility with hydrocarbon fuels Need of upgrading
  • 14. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Bioil platform Bio-oilBIOMASS Catalytic Upgrading HydrodeoxygenationO2 Cracking C6H8O4 + 4 H2 C6H8 + 4 H2O C6H8O4 C4.5H6 + H2O + 1.5 CO2 Gasification H2 / CO Char Activated Carbon Extraction Chemicals Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms”
  • 15. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biogas platform Biogas Organic Waste Anaerobic Fermentation Digestate 55-65 CH4 35-45 CO2 Heat Electricity CHP Cogeneration Fertilizers Compost Gas distribution network Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms”
  • 16. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform : Oil extraction Oil seeds (rape, palm, sunflower, soybean) Dedicated oils crops (Jatropha, algae, ..) Extraction Refining Vegetable Oil Protein Fraction Cattle Feed Refining Crude Oil Lignocellulosic Fraction Sugar Platform Syngas Platform Bio-oil Platform Waste oils (Fried oils, Yellow-grease, …) Non-edible animal fats Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform Oil Transesterification Biodiesel Transport Fuel O O Glycerol Transport Fuel Chemicals Catalytic Cracking Bio-Gasoline Bio-olefins Transport Fuel Chemicals Chemical / Enzymatic modifications Bio-Surfactants Oleochemical-products Hydrogenation Green-Diesel Transport Fuel Proceso Ecofining Eni/UOP
  • 17. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Oil platform: Glycerol chemistry Branched polyesters and nylons OH OH HO Glycerol OH OH HO Glycerol OHHO H3C OH OH CH3 HO HO O CO2H OH HO O O O R1 R2 R3 O OH HO OH OH OH OO O HO O O O O Glycidol 1,3-Propanediol Propylene glycol Propanol Mono-, di-, or tri- glycerate Diglyceraldehyde Glycerol carbonate Glyceric acid Applications: humectant, plasticizer, fibers, solvent, lubricant, sweetener, bodying agent, antifreeze, and fuel formulation. Hydrogenolysis Fermentation Sorona Fiber Antifreeze Humectant Fuels formulation Oxidation Polyester fibers Polycarbonates Polyurethanes Polymerization Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? BIOMASS Sugar Platform “Biochemical” Syngas Platform “Thermochemical” Biogas Platform “Biochemical” Oil crops Platform “Chemical” Pyrolysis “Thermochemical” Sugars Syngas Fuels Chemicals Heat & Power Bio-oil Bio-oil Biogas Oils Lignocelullosic Residues Lignocelullosic Residues • Biorefinery concept is built on different “Platforms”
  • 18. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars extraction Simplesugars (hexosesandpentoses) Starch-rich Biomass Sugar-rich Biomass Extraction Starch Hydrolysis C6 Glucose Lignocelullosic Biomass Chemical/Enzymatic Hydrolysis Cellulose (35-50 %) C6 Glucose Hemicellulose (15-25 %) C5-C6 Forest Residues Agricultural Residues Lignocelullosic Crops Straw Corn Stover Bagasse Lignin (20-25 %) Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars transformation Simplesugars (hexosesandpentoses) Transportation fuels Chemicals
  • 19. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards transportation fuelsSimplesugars (hexoses) C6O6H122C2H5OH+2CO2 FERMENTATION Anaerobic reaction with enzymes 15 % BIOETHANOL DISTILLATION DRYING 96 % Water content 99 % Transport Fuel DDGS Cattle Feed BIOBUTANOL Transport Fuel 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 Lignin Chemical Transformations Added value chemicals Catalytic hydrogenation Current Technology Petroleum Industry J. Zakzeski. “The catalytic valorization of lignin for the production of renewable chemicals” Chem. Rev. 2010 , 110, 3552-3599 Syngas Platform Bio-oil Platform Transport Fuel Heat & Electricity (CHP) Catalytic oxidation More complex molecules Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Sugar platform : Sugars towards 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. Sugars Glucose Fructose Xylose Arabinose Lactose Bio-transformations Chemical Transformation Added value bio-chemicals
  • 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 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 ? Glycerol Chemical routes Hydrogenolysis Oxidation Dehydration Polymerization Etherification Chemical – Transesterification of oilsOH OH HO OH OH HO
  • 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 Sugars Bio- Chemical- Transformations Platform Molecules Added value bio-chemicals Chemical- Transformations Most of them are new processes Most of them are not commercial Most of them are known processes Commercial use Low cost fermentation routes New processes New building blocks Challenges New heterogeneous catalysts to replace homogenous. New catalysts robust towards biomass impurities Use of oxidant of low cost (air, oxygen , …) Challenges
  • 28. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefineries: Future outlook Fuels Chemicals Heat & Power Fossil Sources CmHn CmHnOx Biomass ¿? Yes But … Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? • Biorefineries: Future outlook Challenges & Opportunities New feedstock New processes and products Development of low cost bio-transformation processes (fermentation and enzymatic) New catalysts for this new feedstock New processes for the hydrolysis of lignocelullosic feedstock (more efficient, safe and environmentally friendly) Scaling-up of the processes Biomass valorization can use commercial technology developed for petroleum refining nd petrochemicals Short- Medium- term solution Technologies integration
  • 29. Biorefineries: A sustainable solution to the environmental risks of fossil fuels ? 1st Generation 2nd Generation Biorefinery • Biorefineries: Future outlook 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 Grupo de Ingeniería Química y Ambiental Catalysis for energy: New challenges for a sustainable energetic development Juan Antonio Melero Hernández Catedrático de Ingeniería Química Departamento de Tecnología Química y Ambiental Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?

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