Biodies el production and handling

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Information about Biodies el production and handling

Published on November 7, 2007

Author: fazil


Slide1:  Wenqiao (Wayne) Yuan, Ph.D. Assistant Professor Department of Biological and Agricultural Engineering February 6, 2007 at KFB Biodiesel Production and Handling Kansas State University Slide2:  What is biodiesel Biodiesel Is a renewable fuel Is not straight vegetable oil (SVO) Is not waste vegetable oil (WVO) Is not a mixture of oil/fat with an alcohol Is not a blend with diesel fuel ASTM D6751 Slide3:  100 lbs of oil + 10.86 lbs of methanol -> 100.4 lbs of biodiesel + 10.4 lbs of glycerol A simplified representation of biodiesel production: Transesterification Transesterification (884 g) (96 g) (888 g) (92 g) 100 lbs of oil + 21.72 lbs of methanol -> 100.4 lbs of biodiesel + 10.4 lbs of glycerol Issues Related to Transesterification Process:  Issues Related to Transesterification Process Feedstock Issues FFA Water Process Issues Type of Alcohol Molar Ratio Catalyst Reaction time & temperature Agitation Feedstock Issues:  Feedstock Issues 1. Free Fatty Acids (FFA) Free Fatty acids in the oils react with alkaline catalyst to form soaps. R-OH + KOH K-OR + H2O (FFA) + KOH (Soap) + water It results in loss of catalyst and reduction in yield Feedstock Issues (cont.):  2. Water Water deactivates the catalysts. Drying of oil is required. Water hydrolyses fats to form free fatty acids. Feedstock Issues (cont.) Process Issues:  Process Issues 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 molar ratio is 6:1 for base catalyzed reactions. Type of Alcohol Process Issues (cont.):  NaOH (Sodium hydroxide) High purity KOH (Potassium hydroxide) Need more Glycerol waste can be disposable H2SO4 (Sulfuric acid) Pretreatment of high free fatty acid oil Direct acid catalyzed reaction (not common) Catalyst used Process Issues (cont.) Slide9:  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. Process Issues (cont.) Reaction time, temperature & agitation Batch, Base Catalyzed Process:  Batch, Base Catalyzed Process TG Alcohol Catalyst Batch Reactor Ester Crude Glycerol Alcohol Alcohol Water Water Neutralized Glycerol Wash Water Dryer Biodiesel Water Acid Slide11:  30 gallon biodiesel unit Slide12:  “Appleseed” style biodiesel processor (design by Maria Alovert). Uses old electric water heater as main unit 600 LITERS/DAY BIODIESEL UNIT:  600 LITERS/DAY BIODIESEL UNIT Vacuum Drier Separating Vessel Reaction Vessel Washing Vessel Control Panel Oil Tank Methaoxide Vessel Skid Motor & Gear Box Motor& Gear Pump Development Cost : US $ 7000 High FFA Feed Stocks:  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! Acid Catalyzed Processes:  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 Slide16:  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. Preferred method for High FFA feeds: Acid Catalysis followed by base catalysis Slide17:  Methanol + KOH Vegetable Oil Storage Tank 1500 Kg Methanol + H2SO4 Motor Storage Tank 500 Ltrs. Motor Biodiesel Storage Tank 1000 Ltrs. P2 SV2 Reactor 600 Ltrs. SV2 Air SVO P1 SV3 P3 Settling Tank 1000 Ltrs. Vaccum Drier Separating Column 500 Ltrs./ Charge Washing Column 500 Ltrs./ Charge Vaccum Drier Glycerol Storage Tank 500 Ltrs. Transesterification Reactor, 500Lts./Charge P4 P5 P6 P7 P8 Biodiesel Unit 1tpd Capacity Design by DCE What you need to know about biodiesel:  What you need to know about biodiesel Less energy content:  Less energy content Less energy content 8% less energy per gallon 12.5% less energy per pound 8% less in power and torque 8% more fuel consumption or less MPG For B20, see 1% to 2% reduction in power For B5 or lower, no noticeable differences Stability issue:  Stability issue Long term storage or aging Stability at elevated temperature and/or pressures as the fuel is recirculated through an engine’s fuel system The higher the level of unsaturation, the worse stability is Heat and sunlight will accelerate oxidation Certain metals such as copper, brass, bronze, lead, tin and zinc will accelerate the degradation process Keeping oxygen from the fuel reduces or eliminates fuel oxidation Antioxidants, whether natural or incorporated as an additive, can increase storage life or stability Fuel turn over between 2 and 4 months has no problem NBB recommends 6 month storage life for B100 Cleaning effect:  Cleaning effect Biodiesel has a tendency to dissolve the accumulated sediments in diesel storage and engine fuel tanks, which can plug fuel filters and even burst fuel filters to send all the sediment through the fuel system B35 and above has much greater cleaning effect Even if B20 is fine, it does not justify higher blending level Don’t leave biodiesel on vehicle body Material compatibility:  Material compatibility B100 will degrade, soften, or seep through some hoses, gaskets, seals, elastomers, glues, and plastics with prolonged exposure Nitrile rubber compounds, polypropylene, polyvinyl, and Tygon materials are particularly vulnerable to B100 Contact OEM or dealership before you use B100 Brass, bronze, copper, lead, tin and zinc may accelerate the oxidation of diesel and biodiesel B20 is normally ok Gelling:  Gelling No. 2 diesel B5 is ok B20 is problematic (°C) Biodiesel cold flow:  Biodiesel cold flow Blending biodiesel with diesel is most effective Most cold flow additives have a limited effectiveness on B100, but work with varying degrees of effectiveness with B20 Mix with No.1 diesel fuel in winter Use less saturated feedstock in winter Use B10 or less in winter, but B30 or more in summer Lab testing should be done Summary:  Summary Base catalyzed or acid pretreated and then base catalyzed methods are commonly used to make biodiesel What you need to know about biodiesel: About 8% power and MPG loss Stability issues Cleaning effect Material compatibility Cold gelling Thank you!:  Questions or Comments? Thank you! Wenqiao (Wayne) Yuan Dept of Biological and Agricultural Engineering Kansas State University Office: 785-532-2745 Email: Feedstocks used:  Feedstocks used Soybean oil, rapeseed oil, canola oil, cottonseed oil, corn oil, mustard oil, palm oil, etc Restaurant waste oils such as frying oils Animal fats such as beef tallow or pork lard Trap grease (from restaurant grease traps), float grease (from waste water treatment plants), etc Alcohol used:  Alcohol used Methanol Less expansive Lower boiling point (64.7°C) Toxic Non-renewable Ethanol More expensive High boiling point (78.4°C) Non-toxic Renewable Slide29:  Pure biodiesel-B100 -In European Union Countries Blends (20%)-B20 As an additive-B2 -North Dakota and Minnesota Others: solvents and paint remover } Background How is biodiesel used? Blends (85%)-B85 -Used in a power genset Slide30:  Higher cost Lower energy content Weight base: 12.5% lower, Volume base: 8% lower Worse cold flow properties Higher NOx emissions Background Any problems with biodiesel? Slide31:  Biofuel research opportunities In the U.S. Advanced Energy Initiative: 22% increase in clean energy research funding In Kansas state Kansas alternative fuels bill SB 387 has been introduced in the state Senate by the Committee on Agriculture to require the mandatory use of 2% biodiesel in all diesel fuel sold for IC engines by Jan 1, 2010 Slide32:  Biodiesel Benefits the U.S. Farm Economy Why care about biodiesel? An example of Kansas state once bill SB387 passed Slide33:  Biodiesel benefits the U.S. economy An example of biodiesel impact on Kansas state economy based on an annual diesel consumption of 800 million gal. The U.S. consumes about 60 billion gallons of diesel per year. Slide34:  Cost analysis of biodiesel (analysis from Dr. Jon Van Gerpen) Slide35:  Cost analysis of biodiesel (analysis from Dr. Jon Van Gerpen, Cont.) Example: Farmer Benefits of Biodiesel Use:  Example: Farmer Benefits of Biodiesel Use Assumptions: A farmer wants to support biodiesel prod./use, so he/she uses B5 on-farm at $0.06 more per gal. Soybean increases $0.05/bu because of biodiesel use 30 bu/ac average soybean yield Average of 12.5 gallons of diesel used per acre Gain or Loss = Additional Revenue – Additional Cost Per Acre: 30 bu/ac * $0.05/bu – 12.5 gal/ac * $0.06/gal = $0.75 On All Arkansas Soybean Acres with B5: $2.1 million increase in net returns for AR farmers Example: Farmer Benefits of Biodiesel Use (cont.):  Example: Farmer Benefits of Biodiesel Use (cont.) The break-even soybean price increase is 2.5 cents/bu A less than 1% increase in soybean prices justifies the use of a biodiesel blend fuel. This price increase depends on growth of the biodiesel industry from Voluntary use (e.g. farmers using their own product) Mandatory use (e.g. a federal renewable fuels standard) Example: Farmer Benefits of Biodiesel Use (cont.):  Example: Farmer Benefits of Biodiesel Use (cont.) If all soybean acreage in AR was grown using B5, over 2 million gallons of biodiesel would be demanded Would increase soybean demand 1.45 million bushels. The total amount of diesel used on-farm in AR 2001 was 136.1 million gallons. If B5 was used this would require 6.8 mil gal of biodiesel Would increase soybean demand 4.86 mil. bushels Biodiesel Availability in Arkansas:  Biodiesel Availability in Arkansas Morrilton Agri Coop Supply Neat (100%) biodiesel sells for $1.92/gallon Conventional off-road diesel sells for $0.799 B5 (5% biodiesel) costs $0.056 more per gallon than conventional diesel (0.95*$0.799+0.05*$1.92 = 0.855) World Energy Alternatives will ship to a customer or through existing fuel suppliers Some premium diesel contains small amounts of biodiesel CENEX Ruby Fieldmaster, Roadmaster, and Wintermaster No current biodiesel production in AR Slide40:  Agitated for on hour at 60°C Alkali-catalyzed transesterification Settling for 8 hours for glycerol separation Vacuum stripping Slide41:  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. Molecular structure Slide42:  Catalyst? “Chemical marriage brokers” The presence of a catalyst facilitates reactions that would be kinetically impossible or very slow without a catalyst

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