Biodiesel

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Biodiesel

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Biodiesel

  1. 1. BRINGING AGRICULTURE AND ENERGY TOGETHER December 10, 2010
  2. 2. WHAT IS BIODIESEL?  Fuel from a Source of Oils & Fats...  AN ALTERNATIVE GREEN FUEL…  Fatty Acid Methyl Esters can be used directly as Diesel or Blend with Diesel…
  3. 3. RUDOLF DIESEL Designed Diesel Engine in 1894 to Run on Peanut Oil ““TThhee uussee ooff vveeggeettaabbllee ooiillss ffoorr eennggiinnee ffuueellss mmaayy sseeeemm iinnssiiggnniiffiiccaanntt ttooddaayy.. BBuutt ssuucchh ooiillss mmaayy bbeeccoommee iinn tthhee ccoouurrssee ooff ttiimmee aass iimmppoorrttaanntt aass ppeettrroolleeuumm aanndd tthhee ccooaall ttaarr pprroodduuccttss ooff tthhee pprreesseenntt ttiimmee.."" -An Extract from Diesel’s Speech in 1912
  4. 4. FEED STOCK FOR BIODIESEL • Rapeseed (Germany) • Sunflower oil • Soybean oil (USA & Brazil) • Palm oil (Malaysia) • Linseed, olive oils (Spain) • Cottonseed oil (Greece) • Beef tallow (Ireland), lard, used frying oil (Austria), Jatropha (Nicaragua & South America, India), Guang-Pi (China) • Used oil ( Austria)
  5. 5. WHAT IS BIODIESEL? Fatty Acid alkyl ester prepared from any oil or fat (animal or vegetable source) CH2-O-C O R CH-O-C O R TRANSESTERIFICATION Alkali + Acid Methanol RC O OMe + CH2-OH CH-OH O R CH2-O-C CH2-OH OIL / FAT (TRIGLYCERIDE) Fatty Acid Methyl Ester (Biodiesel) Glycerol R-C O OH ESTERIFICATION + Methanol Acid R-C O OMe Fatty Acid Fatty Acid Methyl Ester · Fatty Acid Methyl ester is a well know molecule for vegetable oil industry · Intermediate for fatty alcohols & oleochemicals
  6. 6. WHY BIODIESEL? • SUSTAINABILITY • POLLUTION THREAT • REDUCTION OF GREEN HOUSE GAS EMISSIONS • REGIONAL (RURAL) DEVELOPMENT • SOCIAL STRUCTURE & AGRICULTURE • SECURITY OF SUPPLY
  7. 7. IMPORTANCE OF BIODIESEL • Environment friendly • Clean burning • Renewable fuel • No engine modification • Increase in engine life • Biodegradable and non-toxic • Easy to handle and store
  8. 8. Comprehensive Emissions Analysis for Biodiesel B20 B100 • NOx 0 +10% • PM -10.1% -47% • HC -21.1% -66% • CO -11.0% -47% • Sulfates -20% -100% (Causes acid rain) • Fuel Economy (B20) -1-2% B20: 20% biodiesel in diesel
  9. 9. BIODIESEL-WHY LOWER EMISSIONS ? • Biodiesel has High Cetane • In Built Oxygen Content • Burns Fully • Has No Sulphur • No Aromatics • Complete CO2 Cycle
  10. 10. PETRO-DIESEL CO2 CYCLE 13 POUNDS OF FOSSIL CO2 RELEASED PER GALLON BURNED Exploration Refining Fossil CO2 Release to Atmosphere Use in Cars and Trucks
  11. 11. BIODIESEL CO2 CYCLE NO FOSSIL CO2 RELEASED ; NO GLOBAL WARMING Renewable CO2 Oil Crops Use in Cars and Trucks Biodiesel Production
  12. 12. DIESEL & BIODIESEL DEMAND, AREA REQUIRED UNDER JATROPHA FOR DIFFERENT BLENDING RATES (Biofuel Document of Indian Govt, 2002) Year Disel Demand MMT Biodiesel @ 5% MMT Area for 5% Mha Biodiesel @ 10% MMT Area for 10% Mha Biodiesel @ 20% MMT Area for 20% Mha 2001-02 39.81 1.99 NA 3.98 NA 7.96 NA 2006-07 52.33 2.62 2.19 5.23 4.38 10.47 8.76 2011-12 66.90 3.35 2.79 6.69 5.58 13.38 11.19 December, 2009 –Indian Biofuel Policy An indicative target of 20% by 2017 for the blending of biofuels – bioethanol and bio-diesel
  13. 13. ROAD BLOCKS FOR BIODIESEL INDUSTRY… · Feedstock Scarcity · Food Vs Fuel Controversy · Initial Enthusiasm Coming Down · Non-edible Oil Production not Encouraging · Effluent-based Traditional Technologies for High FFA Oils · Pricing of Biodiesel is Not Attractive to Anybody · Algal Oils – Long way to go…
  14. 14. WHAT IS THE CHALLENGE? · VERY SIMPLE CHEMISTRY… · Handling multi-feedstock is the real challenge · VERY LOW FFA – only Transesterification CH2-O-C O R CH-O-C O R + Methanol RC Alkali Acid O OMe + CH2-OH CH-OH O R CH2-O-C CH2-OH OIL / FAT (TRIGLYCERIDE) Fatty Acid Methyl Ester (Biodiesel) Glycerol · HIGH FFA – ESTERIFICATION followed by TRANSESTERIFICATION R-C O OH + Methanol Acid R-C O OMe Fatty Acid Biodiesel · > 99% Yields – to achieve good quality FAME – without distillation!! · Recovery of good quality glycerol for economic feasibility · Waste Water Recycling · Good pre-treatment (lower phosphorus ppm levels)
  15. 15. MAJOR CONCERN…FEED STOCK · Present Global Production of Biodiesel ~ 14 million metric tons · Only <50% of Capacity of the Installed Biodiesel Plants Being Utilized… · This Scenario Indicates Several Road Blocks for Biodiesel Industry · Main Concern is the Feed Stock. · Edible Vegetable Oil Expected to Remain the Major Feedstock for the Production of Biodiesel · Countries like India Propagating Non-edible Oils like Jatropha & Karanja, but not Much Progress · Animal Fats and Used Cooking Oils – Several Limitations
  16. 16. GLOBAL MAJOR VEGETABLE OIL SCENARIO Million metric tons VEGETABLE OIL 2005/06 2006/07 2007/08 2008/09 2009/10 Palm 35.98 37.35 41.31 43.19 45.88 Soybean 34.61 36.39 37.51 36.26 37.88 Rapeseed 17.24 17.03 18.31 20.22 22.12 Sunflowerseed 10.59 10.61 9.73 11.46 11.31 Peanut 4.95 4.50 4.83 5.15 4.56 Palm Kernel 4.38 4.44 4.85 5.10 5.50 Cottonseed 4.62 4.86 5.00 4.72 4.66 Coconut 3.47 3.26 3.49 3.64 3.67 Olive 2.66 2.91 2.84 2.97 2.99 Total 118.49 121.33 127.86 132.70 138.57 Source: Oilseeds: World Markets and Trade, USDA, March 2010
  17. 17. 78 39.05 5.06 11.57 20.3 13 14 50 29 13 6 2008-09 44.6 190 million Palm Soybean Rape seed Sunflower Cot tonseed Others. 106 million 2004-05 9.39 33.51 15.96 11.59 5 32.89 134 million @ 7 mt/yr 2019-20 @ 5 mt/yr 30 million 1950’s Change in World Vegetable Oil Scenario…
  18. 18. DISTRIBUTION OF VEGETABLE OIL PRODUCTION IN INDIA OIL 2004-05 MMT 2005-06 MMT 2007-08 MMT 2008-09 MMT 2009-10 MMT Rape / Mustard 2.13 2.27 1.51 2.15 2.05 Soya 0.87 1.07 1.44 1.33 1.28 Groundnut 1.00 0.99 1.17 0.82 0.61 Rice Bran 0.68 0.73 0.80 0.85 0.80 Cottonseed 0.72 0.77 1.05 0.90 1.08 Sunflower 0.55 0.56 0.51 0.40 0.34 Coconut 0.42 0.42 0.42 0.42 0.43 Castor 0.34 0.38 0.41 0.46 0.42 Sesame 0.19 0.13 0.16 0.17 0.21 Niger 0.04 0.02 0.01 0.01 0.02 Safflower 0.06 0.06 0.05 0.05 0.04 Linseed 0.09 0.09 0.08 0.06 0.07 Palm oil 0.04 0.05 0.06 0.07 0.06 Oils from expelled cakes 0.38 0.41 0.47 0.41 0.39 Minor oilseeds 0.08 0.08 0.10 0.10 0.06 TOTAL 7.59 8.03 8.20 8.20 7.88 Source: SEA
  19. 19. INDIAN VEGETABLE OIL PRODUCTION AND IMPORT STATUS (million tones) Year Domestic Edible Oil Production Import of Edible Oils 2009-10 7.9 8.8 2008-09 8.2 8.2 2007-08 8.2 5.6 2006-07 7.72 4.71 2005-06 8.03 4.42 2004-05 7.59 5.04 2003-04 7.78 4.28 2002-03 5.12 5.38 2001-02 6.67 4.42 2000-01 5.81 4.83 Source: SEA
  20. 20. BIODIESEL - INDIAN SCENARIO · Presently importing about 8.8 million tones of edible oil – ~50% of consumption · Clean oils are not available for biodiesel production in the country · Non-edible Oils & Acid Oil – Not more than 5 lakh tones · To wait till Jatropha / Karanja plantation comes to reality - Oil production only after 2 to 3 years!!
  21. 21. TREE-BORNE OILS · Tree-borne oils will be major source for Indian Biodiesel · Most oils are dark · Possess disagreeable smell · Contain non-lipid constituents with variety of structural features · Above problems aggravate by hostile conditions during collection, storage and processing · Depending on the nature of the non-lipid constituents special processing methods have to be developed · Any technology in Indian scenario should take care of multi-feed stocks (high FFA and Unsap)
  22. 22. JATROPHA PLANT WITH SEEDS
  23. 23. KARANJA FLOWERS SEEDS
  24. 24. COMPONENTS RESPONSIBLE (PRESENT IN CURDUE OIL) FOR LOW QUALITY BIODIESEL · Gums · Free fatty acids · Waxes · Unsaponifiables · Pigments
  25. 25. PROCESS FOR BIODIESEL PRODUCTION CRUDE OIL/ DEGUMMED OIL Acid catalyst* Neutralization Transesterification 2-Stage process Neutralization & Distillation Esterification Washing & Drying Distilation *Esterification step is only for high FFA oils Not necessary for low FFA oils Methanol FATTY ACID METHYL ESTER TRIGLYCERIDE Methanol Alkaline catalyst SETTLING TANK FATTY ACID METHYL ESTER GLYCERINE LAYER With Methanol and Alkali METHANOL CRUDE GLYCEROL » 80% BIODIESEL POTASSIUM SULPHATE (Fertilizer)
  26. 26. PRE-TREATMENTS BEFORE TRANSESTERIFICATION TO HANDLE GUMS AND FFA Physical Refining Degumming and Bleaching followed by removal of FFA by Deacidification (High Temperature Distillation) Chemical Refining Removal of FFA using alkali neutralization - Heavy loss of Neutral oil along with Soap (2.5 times of FFA) Esterification Converts FFA to Methyl esters (increases yield of Biodiesel) – Most appropriate option
  27. 27. NEWER APPROACHES · Flexible process for handling variable quality feed stocks with high FFA and unsaponifiables · Efficient conversions using traditional catalysts like NaOH / KOH / H2SO4 · Catalyst-free esterification and transesterification · Application of heterogeneous catalysts for both esterification and transesterification · Biotechnological approaches using lipases · Microbial production of oil or fatty acid methyl ester · Value addition to by-products
  28. 28. ADVANTAGES OF HETEROGENOUS CATALYSTS · Substantial reduction of waste/by-product generation · Savings on catalyst cost – Recycling · Considerably greater increase in reactor throughput · Smaller heat exchange areas – Reduced costs · Greater ease of automation and continuous processing · Sustainable reduction in operating costs · Reduction in chemical use (Catalysts, reagents used to neutralize catalysts) · Reduction in effluents
  29. 29. LIMITATIONS OF REPORTED SOLID ACID CATALYSTS · Most of catalysts reported requires · Higher temperatures · Pressure · Reusability of catalyst not so good · Many of them are water sensitive
  30. 30. LIPASE CATALYZED PREPARATION OF BIODIESEL O O CH2-O-C-R CH-O-C-R O CH2-O-C-R + O Lipase R-COOH + CH3OH R-C-OMe CH2-OH CH-OH CH2-OH Triglyceride FFA Biodiesel Glycerol • Both esterification and transesterification at Room-temperature or less than 50°C • Immobilized enzymes can be recycled upto 20 to 30 times • Still unfavorable for commercial exploitation • Methanol or ethanol denatures the lipase • Lot of scope for biotechnological revolution in this area
  31. 31. GLYCERL-BASED CARBON ACID CATALYST – NEW INNOVATION In situ Carbonization and Sulfonation GLYCEROL + H2SO4 CARBON-ACID CATALYST CARBON-ACID CATALYST INDIAN & PCT PATENTS FILED, 2007 & 2008 ChemSusChem, 2008
  32. 32. CHARACTERIZATION OF GLYCEROL-BASED CARBON ACID CATALYST Powder XRD pattern Scanning Electron Microscope (SEM) image 13C MAS NMR Spectrum FT-IR Spectrum
  33. 33. XSP Spectrum Raman spectrum Elemental Analysis, X-ray Diffraction, SEM, FT-IR, 13C MAS NMR, XSP Spectrum, Raman Spectrum, TG/DTA Analysis, Potentiometric Titration and BET Surface Area SO3H SO3H HO3S CARBON ACID CATALYST OH OH OH GLYCEROL SO3H SO3H SO3H SO3H Conc. H2SO4/ heat SO3H SO3H HO3S HO3S HO3S In situ Carbonization & Sulfonation Characterization…
  34. 34. HOW TO MAKE BIODIESEL CHEAPER? · Efficient Process for Biodiesel Production – Presence of Minimum Amounts of Triglyceride, Diglyceride and Mongoglycerides in the Biodiesel · Phytochemicals & Nutraceuticals of Oil & Other Parts of the Tree (Leaves, Flowers, Bark etc.) · Alternate Applications for Oilseed Cake (Rich in Starch and Protein · Newer Applications for Glycerol
  35. 35. TREE-BORNE LIPIDS & OTHER USEFUL CONSTITUENTS · LEAF LIPIDS - Rich in Biologically Active Constituents - Internal Lipids Acid glycerols, hydroxyl fatty acids etc., - Epicuticular waxes Rich in Hydrocarbons, wax esters, aldehydes, ketones, steryl esters, acetates, fatty alcohols, sterols, triterpenols, fatty acids, etc. · SEED OILS - Edible oils, Structured fats, Industrial Oleochemicals like Biopesticides, Phytochemicals, Nutraceuticals like Gums (lecithin), Tocopherols, Phytosterols, Glycerol · SEED CAKES - Rich Source for protein and starch - Good Fertilizer - Starch and protein based surfactants
  36. 36. KARANJA BIOREFINERY KARANJA SEEDS Bioactive Constituents Cake Oil Lubricant Base Oils & Additives Protein, Starch, Oil Varieties of Products like Surfactants, Lubricants, Fertilizer etc. Fatty Acid Alkyl Esters Crude Glycerol Minor Constituents Lubricant Base Oils & Additives Bioactive Constituents Different Grades of Glycerol Variety of Value Sponsored by Department of Added Products Science & Technology Rs. 18.6 Millions
  37. 37. BIODIESEL PROCESS Esterification Neutralization Transesterification Separation Non-edible Oils with FFA Alcohol + Acid Catalyst Alcohol Alcohol + Base Catalyst Glycerol Biodiesel  Nature of this crude glycerol is different from the glycerol produced by Fat Splitting or the Edible oil-based biodiesel glycerol  Glycerol ~ 50%  Alcohol  Water  Biodiesel  Catalyst  Soap  Salts  Minor Constituents
  38. 38. POTENTIAL DERIVATIVES OF GLYCEROL · Structured Lipids · Oxidation Products · Glyceryl Ethers · Prodrugs · Triacetin, Glycerol carbonate type of by-products (in place of glycerol production)
  39. 39. MAJOR APPLICATIONS OF OILSEED CAKES-PRESENT STATUS  Edible Oilseed Cakes · Source of Protein in Case of Clean Cakes like Groundnut, Soybean, etc. · Animal Feed Formulations  Non-edible Oilseed Cakes · Manure · To Explore for Variety of Applications
  40. 40. JATROPHA / KARANJA CAKES · Huge Quantities of Jatropha / Karanja Cakes if these Plantations Suceed… · Every Tonne of Biodiesel Results in about 2 tonnes of Oilseed Cake · Oilseed Cakes – Real Asset for the Nation as they are Biodegradable · Potential Feedstock – To Make Biodiesel Industry More Attractive · To Develop variety of Products from these Cakes
  41. 41. COMPOSITION OF JATROPHA AND KARANJA OILSEED CAKES Constituent Jatropha Karanja Nitrogen/Protein (wt %) 4-6/25-40 4-7/25-40 Carbohydrate (wt %) 15-20 15-20 Fibre (wt %) 15-20 15-20 Ash (wt %) 3-5 3-5 Phosphorus (wt %) 1.5-3 1-2 Potassium (wt %) 1-2 0.5-1.5 Calcium (wt %) <1 <1 Magnesium (wt %) <1 <0.5 Zinc, Copper, Magnesium, Boron (ppm) <100 <100 Sulphur (ppm) <3000 <4000 * Compositions may not be authentic as all the results are isolated / very old reports
  42. 42. BIOREFINERY OF OILSEED CAKES – POTENTIAL PATHWAYS OILSEED CAKE (BIOMASS) Oil Deoiled Cake Protein Carbohydrates Fertilizer Protein Hydrolysate Surfactants Bioactive Constituents Composite Materials, Surfactants Fermentation Biogas (Methane-rich) Syngas Lubricants, Surfactants, Polymers Bioethanol Fuel, Chemicals Carbon Source for Microbial Lipids / Enzymes
  43. 43. BIOETHANOL FROM CAKES · Currently, Ethanol is made from Corn Grain Starch / Sugarcane Molasses · Newer Feedstocks Required to Meet the Future Demands · Oilseed Cakes / Hulls – Potential Feedstock as they are Made up of Cellulosic Materials · Efficiency of the Pre-treatment and Fermentation Process has to be Optimized based on the Yield of Free Sugars and Ethanol
  44. 44. CARBON SOURCE FOR MICOBIAL GROWTH · For the Production of Microbial Lipids / Non-lipids or Enzymes – Carbon Source Required · Microbial Degradation of Solid Agricultural Waste (Carbon Source) is a Natural Process · Known / Specific Microbial Strains may Produce Desired Products / Enzymes in Presence of a Carbon Source · Oilseed Cakes can be Directly Used as Carbon and Energy Source for Microbial Growth / Production of Desired Products for Many Potential Applications · To Produce Extra Cellular Enzymes such as Proteases, Lipases, Xylanase and Cellulase by Solid-state Fermentation
  45. 45. BIOMETHANATION OF OILSEED CAKES · Several Biogas Plants not in Use for Want of Feedstock · Oilseed Cakes – Excellent Feedstock · 0.25 to 0.35 cubic meters of Biogas can be Produced from 1 kg of Jatropha Cake with » 70-80% Methane Content [Satish Lele (www.Svlele.com)] · Area of Plot, 300m2 ; Manpower, Two unskilled; Power Supply, 1 kw; Cost, Rs. 5 Lakhs · Methane gas – For Generating Electricity – To Promote On-farm Energy Self-sufficiency · Left out Slurry from the Bioreactor – Serves as Organic Manure
  46. 46.  Studies on Physico-chemical Properties of Jatropha/Karanja Seeds (AP State Govt)  60 kg/hr Expeller for Jatropha/Karanja Seeds  Pre-treatment Pilot Plant (15 kg) for Crude Oil  Batch (50 kg) and Continuous (10 kg/hr) Biodiesel Process (AP State Govt & DBT)  Carbon Catalyst from Glycerol for Esterification / Transesterification (CSIR)  Development of Value added products from Karanja oil, cake and glycerol (DST)  Screening of Minor Oils for Biodiesel Production (DST)  Algal Oil-based Biodiesel (Collaborative Project) (DBT, NMITLI)  Exploratory studies on lipase-assisted preparation of biodiesel to enhance Continuous Biodiesel Pilot Plant (10 kg/hr) stability to lipase  Established State of Art Facilities for Vegetable Oils, Biodiesel, Lubricants Research (CSIR, DST) BIODIESEL – IICT’S PROGRAMME Expeller Pre-treatment Plant
  47. 47. Thank you…

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