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![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](https://image.slidesharecdn.com/ma7laitnt3mdgkhvlaah-signature-f555648a221aa96a0ffd63b23897d89f16b326e4a6ed30112ff6e13bc04a9104-poli-141222043347-conversion-gate02/85/Biodiesel-46-320.jpg)
Uploaded byGhassan Hadi
Biodiesel
This document discusses biodiesel, an alternative fuel made from vegetable oils or animal fats. It provides background on biodiesel, including what it is, its benefits over petroleum diesel in terms of emissions and sustainability, and its potential to support agriculture. The document outlines challenges to the biodiesel industry, such as securing stable feedstock supplies, and discusses approaches to overcome issues like handling oils with high levels of free fatty acids. It also examines the current state of the biodiesel industry and potential in India.
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Biodiesel
- 2. December 10, 2010 BRINGINGAGRICULTURE AND ENERGY TOGETHER
- 3. 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…
- 4. RUDOLF DIESEL Designed DieselEngine in 1894 to Run on Peanut Oil ““The use of vegetable oils for engine fuels may seemThe use of vegetable oils for engine fuels may seem insignificant today. But such oils may become in theinsignificant today. But such oils may become in the course of time as important as petroleum and the coal tarcourse of time as important as petroleum and the coal tar products of the present time.products of the present time."" -An Extract from Diesel’s Speech in 1912
- 5. FEED STOCK FORBIODIESEL • 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)
- 6. WHAT IS BIODIESEL? FattyAcid alkyl ester prepared from any oil or fat (animal or vegetable source) CH2-O-C O R CH-O-C O R Alkali Acid + Methanol RC O OMe + CH2-OH CH-OH CH2-OHCH2-O-C O R OIL / FAT (TRIGLYCERIDE) Fatty Acid Methyl Ester (Biodiesel) Glycerol R-C O OH + 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 TRANSESTERIFICATION ESTERIFICATION
- 7. WHY BIODIESEL? • SUSTAINABILITY •POLLUTION THREAT • REDUCTION OF GREEN HOUSE GAS EMISSIONS • REGIONAL (RURAL) DEVELOPMENT • SOCIAL STRUCTURE & AGRICULTURE • SECURITY OF SUPPLY
- 8. 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
- 9. Comprehensive Emissions Analysis forBiodiesel 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
- 10. BIODIESEL-WHY LOWER EMISSIONS? • Biodiesel has High Cetane • In Built Oxygen Content • Burns Fully • Has No Sulphur • No Aromatics • Complete CO2 Cycle
- 11. Exploration Refining Use in Carsand Trucks Fossil CO2 Release to Atmosphere PETRO-DIESEL CO2 CYCLE 13 POUNDS OF FOSSIL CO2 RELEASED PER GALLON BURNED
- 12. BIODIESEL CO2 CYCLE NOFOSSIL CO2 RELEASED ; NO GLOBAL WARMING Biodiesel Production Use in Cars and Trucks Oil Crops Renewable CO2
- 13. DIESEL & BIODIESELDEMAND, 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
- 14. ROAD BLOCKS FORBIODIESEL 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…
- 15. WHAT IS THECHALLENGE? • VERY SIMPLE CHEMISTRY… • Handling multi-feedstock is the real challenge • VERY LOW FFA – only Transesterification • HIGH FFA – ESTERIFICATION followed by TRANSESTERIFICATION • > 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) CH2-O-C O R CH-O-C O R Alkali Acid + Methanol RC O OMe + CH2-OH CH-OH CH2-OHCH2-O-C O R OIL / FAT (TRIGLYCERIDE) Fatty Acid Methyl Ester (Biodiesel) Glycerol R-C O OH + Methanol Acid R-C O OMe Fatty Acid Biodiesel
- 16. 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
- 17. GLOBAL MAJOR VEGETABLEOIL 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
- 18. 39.05 20.3 11.57 5.06 13 44.6 2008-09 15.96 9.39 5 11.59 32.89 33.51 2004-05106 million 134 million @7 mt/yr 2019-20 @ 5 mt/yr 190 million Change in World Vegetable Oil Scenario… 1950’s30 million 78 50 29 13 6 14 Palm Soybean Rape seed Sunflow er Cot t onseed Ot hers.
- 19. DISTRIBUTION OF VEGETABLEOIL 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 Palm oil 0.09 0.04 0.09 0.05 0.08 0.06 0.06 0.07 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
- 20. INDIAN VEGETABLE OILPRODUCTION 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
- 21. BIODIESEL - INDIANSCENARIO • 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!!
- 22. TREE-BORNE OILS • Tree-borneoils 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)
- 23. JATROPHA PLANT WITHSEEDS
- 24.
- 25. COMPONENTS RESPONSIBLE (PRESENTIN CURDUE OIL) FOR LOW QUALITY BIODIESEL • Gums • Free fatty acids • Waxes • Unsaponifiables • Pigments
- 26. Neutralization Transesterification 2-Stage process Neutralization &Distillation Washing & Drying PROCESS FOR BIODIESEL PRODUCTION Distilation *Esterification step is only for high FFA oils Not necessary for low FFA oils Esterification CRUDE OIL/ DEGUMMED OIL Acid catalyst* 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)
- 27. PRE-TREATMENTS BEFORE TRANSESTERIFICATION TOHANDLE 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
- 28. NEWER APPROACHES • Flexibleprocess 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
- 29. 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
- 30. LIMITATIONS OF REPORTED SOLIDACID CATALYSTS •Most of catalysts reported requires •Higher temperatures •Pressure •Reusability of catalyst not so good •Many of them are water sensitive
- 31. LIPASE CATALYZED PREPARATIONOF BIODIESEL CH-O-C-R O O CH2-O-C-R O CH2-O-C-R + CH3OH R-C-OMe O CH-OH CH2-OH CH2-OH Triglyceride FFA Biodiesel Glycerol Lipase R-COOH + • 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
- 32. GLYCEROL + H2SO4CARBON-ACID CATALYST In situ Carbonization and Sulfonation GLYCERL-BASED CARBON ACID CATALYST – NEW INNOVATION INDIAN & PCT PATENTS FILED, 2007 & 2008 ChemSusChem, 2008 CARBON-ACID CATALYST
- 33. Powder XRD pattern 13CMAS NMR Spectrum Scanning Electron Microscope (SEM) image FT-IR Spectrum CHARACTERIZATION OF GLYCEROL-BASED CARBON ACID CATALYST
- 34. XSP Spectrum Ramanspectrum CARBON ACID CATALYST SO3H GLYCEROL OH OH OH SO3HSO3H SO3H SO3H Conc. H2SO4/ heat SO3H SO3H SO3H HO3S HO3S HO3S HO3S In situ Carbonization & Sulfonation Elemental Analysis, X-ray Diffraction, SEM, FT-IR, 13C MAS NMR, XSP Spectrum, Raman Spectrum, TG/DTA Analysis, Potentiometric Titration and BET Surface Area Characterization…
- 35. HOW TO MAKEBIODIESEL 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
- 36. 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
- 37. KARANJA BIOREFINERY KARANJA SEEDS BioactiveConstituents 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 Added Products Sponsored by Department of Science & Technology Rs. 18.6 Millions
- 38. BIODIESEL PROCESS Esterification NeutralizationTransesterification 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
- 39. POTENTIAL DERIVATIVES OFGLYCEROL • Structured Lipids • Oxidation Products • Glyceryl Ethers • Prodrugs • Triacetin, Glycerol carbonate type of by-products (in place of glycerol production)
- 40. MAJOR APPLICATIONS OFOILSEED 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
- 41. JATROPHA / KARANJACAKES • 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
- 42. COMPOSITION OF JATROPHAAND 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
- 43. BIOREFINERY OF OILSEEDCAKES – POTENTIAL PATHWAYS OILSEED CAKE (BIOMASS) Oil Deoiled Cake Protein Carbohydrates Composite Materials, Surfactants Fermentation Biogas (Methane-rich) Syngas Bioactive Constituents Carbon Source for Microbial Lipids / Enzymes Protein Hydrolysate Surfactants Fertilizer Bioethanol Fuel, Chemicals Lubricants, Surfactants, Polymers
- 44. 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
- 45. CARBON SOURCE FORMICOBIAL 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
- 46. BIOMETHANATION OF OILSEEDCAKES • 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
- 47. Continuous Biodiesel PilotPlant (10 kg/hr) 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 stability to lipase Established State of Art Facilities for Vegetable Oils, Biodiesel, Lubricants Research (CSIR, DST) BIODIESEL – IICT’S PROGRAMME Expeller Pre-treatment Plant
- 48.