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Biodiesel- An outline
- 3. What? An oxygenated, sulfur-free, biodegradable, non-toxic, and eco-friendly alternative diesel oil. Chemically - a fuel composed of mono-alkyl esters of long chain fatty acids derived from renewable sources, such as vegetable oil, animal fat, and used cooking oil designated as B100.* Remember!! ASTM and European standards. *Source: ASTM D6571
- 4. Rudolf Diesel, Pioneer of Age of the Power “The diesel engine can be fed with vegetable oils and would help considerably in the development of agriculture of the countries which use it” and that “The use of vegetable oils for engine fuels may seem insignificant today. But such oils may become in course of time as important as petroleum and the coal tar products of the present time.” Source: dieselnews.wordpress.com
- 6. Different sources same property!! EdibleOil • Castor Oil • Coconut Oil • Soyabean Oil • Peanut Oil • Palm Oil • Mustard Oil • Sunflower Oil • Rapeseed Oil Non-Edible • Jatropha Oil • Jojoba Oil • Pongamia Oil • Copaiba Oil • Paradise Oil AnimalFat • Tallow • Lard • Chicken Fat • Animal Fat Mix
- 8. Esters of glycerol and fatty acids Lipids Fatty acids and alcohol Simple Unsaturated/saturated fatty acid + glycerol Fats and Oils Fatty acids + mono or dihydric alcohol Waxes Simple + Phosphoric acid, sugars, sphingosine etc. Compound Phosphoric acid+ Nitrogenoeus Base Phospholipids Hydrolytic products of simple and compound lipids Derived Free long chain fatty acids Fatty acids Glycerol and other sterol Alcohol Based on Products of Hydrolysis
- 9. Fatty Acids Saturated Unsaturated Polyunsaturated Omega3 Soybean Rapeseed Omega6 Corn oil Sunflower oil Monounsaturated Omega9 Olive oil Peanuts
- 10. Fatty acid content Fatty acid Chemical Formula Lauric (12:0) CH3 (CH2)10 COOH Palmitic (16:0) CH3 (CH2)14 COOH Estearic (18:0) CH3 (CH2)16 COOH Oleic (18:1) CH3 (CH2)7 CH = CH (CH2)7 COOH Linoleic(18:2) CH3 (CH2)4 CH = CH CH2 CH = CH (CH2)7 COOH Linolenic(18:3) CH3 CH2 (CH = CH CH2)3 (CH2)6 COOH Ricinoleic (18:1) CH3 (CH2)5 CHOH CH2 CH = CH (CH2)7 COOH Oil/Fat SFA (% w/w) NSFA ( % w/w) Soybean 14 86 Palm 49 51 Peanut 17 83 Yellow Grease 33 67 Beef tallow 48 52
- 11. Triglycerides • Ester • 3 fatty acids bond to a glycerol Oil Type Palmitic acid Myristic acid Stearic acid Oleic acid Linoleic acid Soybean Palm Peanut Jatropha Source: http://www.chempro.in/fattyacid.htm
- 12. Biodiesel Vs Petroleum diesel Petrodiesel: 95 percent saturated hydrocarbons and 5 percent aromatic compounds Biodiesel: Fatty acid methyl esters (FAME) Source: Energy fact sheet, Penn State University
- 13. Biodiesel Vs Petroleum Diesel Higher lubricity (Reduce Engine Wear) Much less toxic Practically no sulphur Higher oxygen content (10- 12%) More likely to oxidize (react with oxygen) to form a semisolid gel-like mass Tends to thicken and “gel up” at low temperatures more readily More chemically active as a solvent Source: Energy fact sheet, Penn State University
- 15. Vegetable Oil to Biodiesel Treatment of Raw material Transesterification Separation Purification Upstream Downstream Source: Springer books, Introduction to Biodiesel Production
- 16. Treatment of raw materials Extraction Refining Rendering Mechanical Pressing Volatile Solvents Degumming Phosphotides Neutralizing Di/Mono Glycerides, Protein matter, Resins, FFA Bleaching Colouring matter Source:http://www.chempro.in/processes.htm
- 17. WHY TREATMENT? Highest glycerin quality and yield Higher economy of the plant Optimum cold stability Output: Straight vegetable oil
- 18. What makes it bio-”Diesel”? Transesterification!! FAME
- 19. Raw materials Required Alcohol-to-oil Volume Ratio, 1:4 (R = 0.25) Catalyst Basic: Sodium hydroxide (NaOH), potassium hydroxide (KOH), carbonates. Acid: Sulfuric acid, sulfonic acids and hydrochloric acid Enzymatic: Lipases Alcohol Most widely used: Methanol (CH3OH) and Ethanol (C2H5OH). Methanol: Most widely used. Petrochemical origin. Ethanol: Less used, more complex production technology. Biomass origin. Source: Springer books, Introduction to Biodiesel Production
- 20. Conversion of an ester (vegetable oil or animal fat) into a mixture of esters of the fatty acids that makes up the oil (or fat). Transesterification Catalyst should be completely mixed with the alcohol to form alkoxide. Alcohol-Catalyst Mixing Oil is mixed with alkoxide, Carried out a higher temperature(50-60oC) and under continuous stirring. Chemical Reaction Alcohols and oils do not mix at room temperature Source: Springer books, Introduction to Biodiesel Production
- 21. Separation • What? From glycerol (1.28) and unused reactants such as methanol (0.79) and catalyst (0.97), and any solids that may have formed. • How? Liquid-liquid separations- phase separation Separation Centrifugation Physical separation Source: Springer books, Introduction to Biodiesel Production http://www.biodieselmagazine.com/ 0.88
- 22. Purification • Removal of remains of methanol, catalyst and glycerin – water soluble. • Avoid the formation of emulsions during the washing steps. • After drying, the purified product is ready for characterization as biodiesel according to international standards Wash with water Neutralize the esters- with acidified water Dried to eliminate traces of water Source: Springer books, Introduction to Biodiesel Production
- 23. Terminology • Cloud Point: Temperature at which dissolved solids are no longer completely soluble, precipitating as a second phase giving the fluid a cloudy appearance. • Pour Point: Temperature at which it becomes semi solid and loses its flow characteristics • Flash Point: Lowest temperature at which it can vaporize to form an ignitable mixture in air • Cetane Number: An indicator of the combustion speed of diesel fuel.
- 24. Standards Specifications American ASTM D6571 European EN14214 Petroleum Diesel EN 590:1999 Flash Point 93 0C 120 0C 55 0C Cetane Number 47 51 51 Sulfur Content 15 mg/kg 10 mg/kg 350 mg/kg Water Content 500 mg/kg 500 mg/kg 200 mg/kg Total Glycerine 0.24 % mass 0.25% mass Density 0.86-0.90 g/cm3 0.82-0.845 g/cm3 Viscosity 1.9-6.0 mm2/s 3.5-5.0 mm2/s 2.0-4.5 mm2/s
- 27. Engineering Aspects Planning Process plant size Plant site selection Location Feedstock sourcing Biodiesel Marketing Glycerine Outlet Critical parameters Operating/ Capital Costs Safety Quality Uptime/ Downtime
- 28. Environmental Issues NOx Emission Movement of agrichemicals
- 29. Economics Economic Assessment Resource Availability Financial Analysis Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
- 30. Resource Availability Land Requirement • Wasteland (32.2 millon ha) • 20 million ha = 20 million tons of oil (biodiesel) Water Requirement • Minimum rainfall of 600 millimeters (mm) Wasteland Selection Criteria Annual rainfall > 600 millimeters. pH of the soil < 9. Temperature > 0°C and frost conditions should not prevail. The slope of land < 30°. The land should not be waterlogged. The land should not be barren or rocky. Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
- 31. Financial analysis Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
- 32. Biodiesel Supply Chain- Critical Bottlenecks Supply- Chain Segment Critical Bottlenecks Nursery Lack of high-yielding varieties and, good-quality planting material; and high variation in yields Plantation and harvesting • Limited land availability and allocation • Agronomic and management practices that are not fully developed • Absence of minimum procurement price of seed • Long gestation period; no revenue in first few years • High labor cost of harvesting • Uncertainty about the future of the industry Oil extraction • Higher cost of extraction due to low capacity utilization • Inadequate supply of seeds • Dispersed feedstock production, limiting economies of scale Trans-esterification • Higher cost of trans-esterification due to low capacity utilization • Shortage of feed stocks • Dispersed feedstock production, limiting economies of scale • Uncertainty in the biodiesel industry Blending and retailing • Non-remunerative prices set by OMCs, which are not revised regularly • Opposition of OMCs to direct retailing of biodiesel by other Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
- 33. Safety Procedures • Biodiesel plants use a considerable quantity of highly flammable liquid (methanol) & corrosive material (sodium methoxide). • Process plant: Designed as a hazardous area environment- defined by NFPA-497 (NFPA-National Fire Protection Association). • Methanol and sodium methoxide storage tanks must be designed in accordance with NFPA 30. • NFPA 497- • Criteria to determine ignitability hazards in chemical process areas using flammable liquids, gases, or vapors to assist in the selection of electrical systems and equipment for safe use in classified locations. • NFPA 30- • Safeguards to reduce the hazards associated with the storage, handling, and use of flammable and combustible liquids. Source: www.nfpa.org
- 34. Policies and Regulations Policy : 1. Central role for Biodiesel 2. Accelerated development and promotion - cultivation, production and use of 3. Substituting petrol and diesel with bio- diesel for transport. 4. Creating new employment opportunities and leading to environmentally sustainable development. Approach: 1. Target of 20% blending of biofuels by 2017. 2. Focus to utilize waste and degraded forest and non-forest lands and non-edible oil seeds for production of bio-diesel. 3. Cultivators, farmers, landless laborers etc were encouraged to undertake plantations that provide the feedstock for bio-diesel. 4. Corporates were also enabled to undertake plantations through contract farming by involving farmers, cooperatives and Self Help Groups etc. Distribution & Marketing 1. Responsibility (Storage, transport and distribution) - OMCs. 2. The entire value chain- determining the bio- diesel purchase price. Source: National Policy on Bio-fuels,2009
- 35. Pros Environment Friendly- No sulfur dioxide production Rural employment generation High Cetane Number Emission Control Extends the life of diesel engines 90% reduction in risk of cancer and neonatal defects Bio- degradable (within 28 days in water)
- 36. Cons 1.5 times expensive than normal diesel Higher fuel consumption Higher freezing point May degrade plastic and rubber hoses May lead to fuel filter clogging Distribution infrastructure needs improvement
- 37. Biodiesel can be used in blends with diesel fuel
- 38. Biodiesel Blends Blend % Biodiesel Engine Modification Application B100 100 Yes Diesel Engines B20 20 No Rail EnginesB5 5 B2 2
- 40. Why Jatropha? Non-edible Oil Drought Resistant Cheaper feedstock Non-forest area for cultivation High Oil Yield: Soybeans- 280 gallons per acre Rapeseed - 740 gallons per acre Jatropha - 2,226 gallons per acre Source: www.jatrophabiodiesel.org/
- 41. Comparison of Base and Enzyme Catalysis Catalyst Base Enzyme Reaction temperature 60-70°C 30-4OoC Free fatty acids in raw materials Saponified products (soap formation) Methyl esters Water in raw materials Interference with the reaction No influence Yield of Methyl esters Normal Higher Recovery of glycerol Difficult Purification of methyl esters Repeated washing None Catalyst cost Cheap Relatively expensive
- 42. Current Research in India Source: http://www.eai.in/ Phycological Society of India Central Salt & Marine Chemicals Research Institute DBT‐ICT Centre for Energy Biosciences, Institute of Chemical Technology Indian Council of Agricultural research The Energy and Resource Institute The International Crops Research Institute for the Semi- Arid Tropics (ICRISAT)
- 43. Biodiesel Related Companies in India Source: http://dbtjatropha.gov.in/companies.php
- 44. Biodiesel in India • Shatabadi Express ran on 5% bio-diesel from Delhi to Amritsar on 31st December 2002. • Five hundred government buses in Mysore are proposed to be run on biodiesel as per proposals cleared by Karnataka Cabinet. • The Indian Railways has put forward plans to set up four biodiesel plants costing about Rs 1.2 billion. • A research project in India has fuelled a Chevrolet diesel Tavera on a 20% biodiesel blend made from marine micro algae. • The project was part of the New Millennium India Technology Leadership Initiative (NMITLI) with researchers from the Ministry of Earth Sciences (MoES) and Council of Scientific and Industrial Research (CSIR).
- 47. Conclusion Economically viable Can generate sizable employment opportunities Production is limited to wasteland, the food sector will not be adversely affected. Significant potential to reduce carbon emissions and generate carbon revenues. Government interventions : Research on the agronomy of oilseed plants Allocation of wasteland Establishment of a dedicated agency for biodiesel Provision of an incentive package for private investors & small-scale producers