BIODIESEL PRODUCTION TECHNOLOGY & FEEDSTOCKS FOR INDIA Expert Lecture at Workshop on Moving Toward Sustainable Energy Systems: Exploring Global Pathways to a Common Destination Organized by UNIVERSITY OF MINNESOTA, OCTOBER 24,2006 PROF. NAVEEN KUMAR COORDINATOR, BIODIESEL RESEARCH DELHI COLLEGE OF ENGINEERING DELHI, INDIA Email: naveenkumardce@rediffmail.com Phone : 27871248, 32924637 Mobile : 9891963530, 9810363530 What is Biodiesel? Biodiesel, a fuel composed of mono-alkyl esters of long chain fatty acids derived from variety of vegetable oils or animal fats, designated as B100, and confirming to different quality standards e.g. ASTM D 6751, EN14214 or IS 15607. Transesterification Reaction 1 triglyceride + 3 alcohol catalyst 3 ester alcohol + 1 glycerine Me O= O O= O O= O O= 3 MeOH Me O O= Me O O= O HO HO KOH Catalyst Triglyceride HO Glycerol Biodiesel (Methyl Ester Alcohol) Molecular Structure Fats and oils have quite big molecules with a spinal of glycerol on which are bond three fatty acid rests. By the transesterification, the fatty acid rests are removed from the glycerol and each is bond with methanol. The products are one mole glycerol and three mole of fatty acid methyl ester. Issues Related to Base Catalyzed Transesterification Process Feedstock Issues FFA Water Process Issues Type of Alcohol Molar Ratio Catalyst Reaction time & temperature Agitation Feedstock Issues 1. Free Fatty Acids (FFA) Free Fatty acids in the oils react with alkaline catalyst to form soaps. R-OH + KOH Acid + KOH K-OR + H2O Soap + water It results in loss of catalyst and reduction in yield Feedstock Issues 2. Water Water deactivates the catalysts. Drying of oil is required. Water hydrolyses fats to form free fatty acids. Free fatty acids react with alkali catalysts forms soaps Soaps semi solid mixture glycerol separation Process Issues Type of Alcohol • Methanol, Ethanol, Butanol etc • Methanol –commercially used • In methanolysis, emulsion forms and separated into lower glycerol portion and upper ester portion. Reaction time is small • In ethanolysis, emulsions are stable and requires more complicated separation and purification process. Reaction time is large • Typical alcohol: TG ratio is 6:1 for base catalyzed reactions. Catalyst? “Chemical marriage brokers” The presence of a catalyst facilitates reactions that would be kinetically impossible or very slow without a catalyst Homogeneous versus Heterogeneous Homogenous The catalyst, reactants and products are all in one phase, normally the liquid phase. The reactions proceed over a intermediate complex and are often highly selective, but separation of the products and the catalyst is difficult. Hetrogenous The catalyst is in one phase, normally solid, while the reactants and products are in another phase. Separation of catalyst and products is easy, but the reaction is often less selective, because the catalyst material is not homogeneous Various Catalysts used in Biodiesel Production Homogenous • Base Catalysts: NaOH, KOH, NaMeO • Acid Catalysts: H2SO4, PTSA, MSA, H3PO4, CaCO3 Typical base concentrations are : NaOH/KOH – 0.3 to 1.5 % Na MeO – 0.5 % or less Heterogeneous • Sulfated Zeolites & Clays • Hetro-poly acids • Metal Oxides, Sulfates • Composite materials Reaction time , Temperature & Agitation Transesterification reaction will proceed at ambient (30°C) temperatures but needs 4-8 hours to reach completion. Reaction time can be shortened to 2-4 hours at 40°C and 1-2 hours at 60°C. Higher temperatures will decrease reaction times but require pressure vessels because methanol boils at 65°C. Better agitation should be adopted to accelerate reaction. Batch, Base Catalyzed Process Alcohol TG Water Water Ester Biodiesel Alcohol Dryer Catalyst Water Alcohol Batch Reactor Wash Water Acid Crude Glycerol Neutralized Glycerol 10 Liters Biodiesel Unit Stirrer Water Cooled Condenser Cooling Water Reaction Vessel Heating Element Development Cost : US $ 1300 600 LITERS/DAY BIODIESEL UNIT Control Panel Motor & Gear Box Skid Oil Tank Methaoxide Vessel Washing Vessel Reaction Vessel Vacuum Drier Separating Vessel Development Cost : US $ 7000 Motor& Gear Pump High FFA Feed Stocks Biodiesel feed stocks are classified by the amount of free fatty acids they contain: • Refined vegetable oils < 0.05% • Crude vegetable oil 0.5-5% • Used Cooking Oil 2-7% • Animal fat 10-30% Price decreases as FFAs increase but processing cost also increase Base Catalyzed Reaction not suitable for high FFA feeds because of soap formation. Most of the non-edible oils available in India contains high FFA (212%) & to decrease the cost of biodiesel, it is imperative to utilize high FFA oil or fatty acids Acid Catalyzed Processes Acid catalyzed processes are used for direct esterification of free fatty acids in a high FFA feedstock Limitations: Water formation by FFA + methanol ==> methyl ester + water High alcohol: FFA ratio required – about 40:1 Large amounts (5 to 25 %) catalyst may be required Preferred method for High FFA feeds: Acid Catalysis followed by base catalysis Use acid catalysis for conversion of FFAs to methyl esters, until FFA < 0.5%. Acid esterification of FFA is fast (1 hour) but acid catalyzed transesterification is slow (2 days at 60°C). 2. Then, add additional methanol and base catalyst to transesterify the triglycerides. 1. Air SVO P1 Methanol + H2SO4 SV2 P3 P2 Vaccum Drier Motor SV3 P8 Settling Tank 1000 Ltrs. Reactor 600 Ltrs. Motor Vegetable Oil Storage Tank 1500 Kg Biodiesel Storage Tank 1000 Ltrs. Design by DCE SV2 Biodiesel Unit 1tpd Capacity P7 Vaccum P6 Methanol + KOH Storage Tank 500 Ltrs. P5 Drier P4 Glycerol Storage Tank 500 Ltrs. Washing Column Separating Column 500 Ltrs./ Charge 500 Ltrs./ Charge Transesterification Reactor, 500Lts./Charge Barriers to Homogeneous Catalyst Sensitivity to FFA & water content of the feedstocks Removal of catalyst Formation of soap with high FFA feedstock Large quantity of effluent water as a result of removal of catalyst Necessities pre-treatment of oil in case FFA content are higher No scope for regeneration or re-utilization Heterogeneous Catalyst Benefits - Heterogeneous Catalyst Catalyst Regeneration – Decrease of Catalyst Cost Utilization of lower quality feed stocks for biodiesel production Simplification of separation process – Decrease of production cost Decrease of wastewater – Development of environmental friendly process Product Quality Product quality is important – modern diesel engines are very sensitive to fuel. It is not biodiesel until it meets Quality Standards. Reaction must be >98% complete. Acid number – for degrading, oxidized fuel Flashpoint – for residual methanol Water & sediment – fuel fouling, deposits Sulfated ash – for residual catalyst Total glycerin – for incomplete conversion, detects residual mono, di and tri glycerides Free glycerin – inadequate fuel washing Feed Stocks for India Feed stocks used in different Countries Feedstock Countries Rape seed , Sunflower EU Soya bean U.S.A. Palm Oil Malaysia Coconut Philippines Linseed & Olive oil Spain Cotton Seed Oil Greece Jatropha Curcas Oil Nicaragua Used Cooking Oil Japan Beef Tallow Ireland , USA Used frying Oil Australia WHY JATROPHA THE SUITABLE CHOICE ? Thrives on any type of soil Needs minimal inputs or management Has no insect pests Not browsed by cattle or sheep Can survive long periods of drought Propagation by seed/cutting is easy Rapid growth Yield from the 2nd year onwards Yield from established plantations 5 tonne per ha. 30% oil from seeds by expelling Seed meal excellent organic manure Target Output per Hectare Estimated Biodiesel production per Hectare = 3,000 litres/700Gal 2500 trees per hectare produces Seed 6.9 tonnes Seedcake 4.2 tonnes Vegetable Oil 2.7 tonnes Glycerol 0.27 tonnes Potential yields of 12 tonnes per hectare and 55% oil Extraction are also attainable Anti-Erosive Properties Reduces wind and water erosion of soil Improved absorption of water by soil Properties of press cake as fertilizer Quality seedling preparation 10 x 20 cm bag Germination -3 days 3-6 months old seedlings VIEW OF JATROPHA PLANT NURSERY Intercropping with Jatropha Indian Biodiesel Program Name of Biodiesel started making appearance at Indian Conferences, Workshops & Seminars in 1999 ‘Report of the Committee on Development of Biofuel’ – Planning Commission, GOI in 2003 Stage I ‘Demonstration Project’ use Jatropha curcas on 400,000 ha (0.5 MMT BD) Nation-wide investment $ 300mn Stage II – 11 mill ha (13 MMT biodiesel) for 20% blend. Demonstration project started with initial grant of $11mn for nursery raising rest is expected to be sanctioned late this year First 10,000 TPA plant in Hyderabad about to start production Garware100,000 TPA DMT plant modified for biodiesel production A 250,000 TPA plant is being setup in Vishakhapatnam , A.P. A 100,000 TPA plant is coming up in Kakinada , A.P. India’s target of bio-diesel production 5 % mixing of Biodiesel in HSD by 2007 20 % mixing of Biodiesel in HSD by 2012 Diesel & Biodiesel Demand, Area Required under Jatropha For Different Blending Rates Year Diesel Demand (MT) Biodiesel requirement for blending (MMT) @ 5% @ 10% @ 20% Area Requirement for Blending (Mha) @ 5% @ 10% @ 20% 2006-07 52.33 2.62 5.24 10.48 2.19 4.38 8.76 2011-12 66.90 3.35 6.69 13.38 3.35 5.58 11.19 Land requirement for different blending percentages Summary Biodiesel is an renewable fuel for diesel engines that can be made from virtually any oil or fat feedstock. Biodiesel with a potential consumption of 15000 million litres can have a retail turnover of more than US$ 9000 mn per year It can provide huge rural employment potential of 40 to 50 million families and transform the rural economy Remote village electrification and power for agriculture application – Energy grown & used by village. The technology choice is a function of desired capacity, feedstock type and quality, alcohol recovery, and catalyst recovery. Summary The dominant factor in biodiesel production is the feedstock cost which around 70%, with capital cost contributing only about 7 % of the product cost. Therefore high FFA, lower quality feedstock should be promoted for biodiesel production in India. For meeting energy security and electricity for all, it is necessary to develop and commission small to medium capacity biodiesel unit at village & community level.. Maintaining product quality is also essential for the growth of the biodiesel industry in India. Thank You all for your precious time