MERC Biodiesel production by esterification of non-edible oils Control Number: 94 *Farah Halek, Azarmidokht Hosseinnia, Ali Kavousirahim Materials and Energy Research Centre (MERC), Tehran, Iran
Energy Use What do we use energy for? Heating & Cooling Lights, appliances, industries,cooking, household uses Manufacturing Transportation Gasoline Diesel (Biodiesel can be used to supplement or replace diesel fuel) 2
Biodiesel as an alternative fuel Fluctuation of increases in crude oil prices, limited recourses of fossil oil, environmental worries, population increase and hence, higher energy demand, biodiesel represents a promising alternative fuel for use in compression ignition (diesel) engines.
What Is Biodiesel? Biodiesel is a diesel fuel made from vegetable oil, used cooking oils, alga and methanol and a catalyst. Biodiesel is the only alternative fuel that has passed all of the EPA clean air fuel requirements. Biodiesel is fully compatible with any diesel engine. Biodiesel is safe to handle and is biodegradable, it is less toxic than table salt.
Continued Chemically: Long chain fatty acid mono alkyl esters Exact chemical composition difference for different sources of oil. Its a good solvent
Continued Raw material crops for Bio energy were mainly edible crops oils such as Cloza, soybean, rapeseeds, palm, canola, mustard, corn and waste cooking oils Affects the international grain price Noted that it may agitate food shortage problems in underdeveloped and developing countries Necessity of non-edible material crop development Active support is required particularly for non-edible oil crops that are less p affected by the international grain
Benefits of Biodiesel Environmental (Air, Water, Waste) Energy Independence (Domestic, Renewable) Economic/Cost (Waste to Fuel) Quality/Standards Energy Policy Compliance Biodiesel makes a great degreaser The flash point of biodiesel is above 200 C (of petrodiesel is 70 C) Therefore biodiesel and dieselblends are safer to store, handle, and use than conventional diesel fuel. 7
What are pollutant emissions? Regulated pollutants: t Carbon monoxide (CO) apoison Hydrocarbons (HC) causes formation of ozone Particulate matter (PM) soot and aerosols Nitrogen oxides (NO x ) causes formation of ozone and fine particles For diesel; PM, CO,HC, CO 2,SO 2 are really important Unregulated pollutants: t Aldehydes highly reactive for ozone, have health effects Polyaromatic hydrocarbons (PAH) known carcinogens Nitro-PAH known carcinogens
Biodiesel s Effect on Emissions Older Engines EPA analysis: data from many studies engine models through 1997 NO x No change for B5 2% up for B20 10% up for B100 PM 5% down for B5 12% down for B20 48% down for B100 Analysis from EPA420-P-02-001, October 2002
Comparison of pollutant emissions from biodiesel and diesel fuels B100 ** B20 Diesel CO2 Mutagenicity n-pahs PAHs Sulfates **NOx Particulate Matter CO Total Unburned HCs 0 20 40 60 80 100 120 Percent ** B100 (100% biodiesel) with NOx adsorbing catalyst on vehicle
Biofuel: a Better Fuel vs. Diesel Higher cetane Greater lubricity Superior detergency Higher flash point Features More mileage Greater horsepower Less smoke Smoother running engines Quicker starts Longer engine life Reduced maintenance Benefits
Why Use Biodiesel? Amount of fossil energy used in biodiesel production is similar to that used in petroleum production A small fraction of fuel energy-truly renewable
Obstacles to Biodiesel Acceptance Oil quality is more important Limited supply Due to both demand and supply reasons Potential increase of NOx emissions Lack of familiarity 13
Biodiesel Production Process: Transesterfication Methanol Oils & Fats (Feedstock) Catalyst Methanol Recovery Transesterification Purification Water Methyl Esters (biodiesel) Glycerin, Water & Methanol Glycerin Glycerin & Water Glycerin & Methanol
Experimental: Transesterification Reaction Catalyst Solvent Vegetable Oil Methanol Methyl Esters Glycerin
Experimental Conditions The common transesterification method was Adapted for conversion of the colzy non-edible oil to the biodiesel fuel. R1, R2, and R3 are fatty acids (could be different, or the same), anddepend on the type ofoil.the fatty acids involved determine the final properties of the biodiesel (Cetane number, cold flow properties, etc.) For producing the biodiesel oil, 10 different reactions were carried on, using different ratios of colzy oil, methanol, catalyst (sulfuric acid). The optimum temperature of the transesterification was 63 C and the time of the reaction was 1.5 hr.
Experimental Conditions (Continued) Using these optimum conditions, the yield of converting the base oil to the esterified oil was reached to 93.5 %. The optimum ratio of the oil/alcohol was 0.1/1. Different catalysts (acidic, basic, nano and enzymes) could be used in this reaction. In this experiment, sulfuric acid, which is cheap and produced in Iran, was chosen and used. The optimum amount of sulfuric acid was found to be 1.8 % of the base oil.
Some of the characteristics of colzy oil feedstock Test Value Boiling Point (ºC) 280 300 Density (g/cm 3 ) 0.912 Water Content (%) 004 0.04 Fatty Acid Contents (%) : Linoleic (C 18 H 32 O 2 ) 59.8 Oleic (C 18 H 34 O 2 ) 24.96 Palmitic (C 16 H 32 O 2 ) 587 5.87
Transesterification reaction
Product of reaction
ASTM International Specifications
Specifications of the colzy oil based biodiesel Property Standard no (Value) Biodiesel Flash Point (ºC) Water Content and precipitates (% value) Kinetic Viscosity (mm 2 /s) D93(180) D2709(0.05) D445(1.9-6) 208 0.042 283 2.83 Copper Corrosion Cetane No. D130(3) D613(47) 2 49 Pour Point (ºC) Color Heat value(mj/kg) D97 D1500-15 1.5 46.7
Effect of Biodiesel Blending on Diesel Properties Cetane number increases Better combustion, lower emission Lubricity improves Protection to fuel injection equipment Lower Flash point More safety Kinematic Viscosity Higher but within range, better protection to fuel injection equipment Low Sulphur content LowerSO 2 and Particulate emission 2 Storage stability and material compatibility could be of concern need further investigation.
Engine Tests Efficiency i of the biodiesel oil was evaluated, using an agricultural engine. For loading the engine, it was connected to a 400 kw chassis dynamometer. In the experiment an emission analyzer (Orast analyzer, model AVL4000, Belgium) was used in order to analyze the engine exhaust pollution parameters. This test t component measures CO 2 emission in volume percentage, CH, CO and NOx in parts per million (ppm) and exhaust smoke in mg/m 3.
Engine Tests (Continued) Testing started after engine warmed up and reached the steady state t (20-30 min). Engine cycle reached an average and then the maximum values at speed 1400 to 2000 cycle/min respectively and then exhaust emission and engine torque were analyzed by smoke analyzer and dynamometer.
Engine Specifications (M4-244) Company Engine volume (lit) Maximum power (hp) Maximum torque (nm) Turning direction Electric system (v) Cooling system Diameter x Piston course (mm) Combustion system Combustion ratio Air inlet system Iranian Tractor Company 3.99 82 1300 Clockwise 12 Water and oil 127 x 100 Direct injection 17.5 : 1 Turbo charger
Engine (M4-244)
Test Working Place
Dynamometer (400 kw, magnetic)
In this test 400KW Eddy current magnetic dynamometer made in Belgium were used to measuring the MT4-244 engine's power and torque. Dynamometer measuring process was done according to ISO-3046 standard and the torques was measured automatically by applying magnetic field and the result represented as data.
Emissions Analyzer
Results CO is the result of incomplete ignition in air lack situation and the quantity of CO pollution is greatly depends d on mixing portion. High deference in various periods is because of Air/Fuel portions.
Comparison of CO emissions from biodiesel and diesel fuels 3000 2500 CO (p ppm) 2000 1500 1000 500 B20D80 B10D90 B5D95 D100 0 1400 2000 R P M
Comparison of CO 2 emissions from biodiesel and diesel fuels 14 12 (ppm) CO 2 10 8 6 4 2 B20D80 B10D90 B5D95 D100 0 1400 2000 1400 2000 R P M
Percentage of CO 2 emission reduction using biodiesel fuel 0 D100 B5D95 B10D90 B20D80-5 % CO 2-10 -15 1400 rpm 2000 rpm -20-25
Comparison of HC emissions from biodiesel and diesel fuels HC (ppm) 9 8 7 6 5 4 3 2 1 0 1400 2000 R P M B20D80 B10D90 B5D95 D100
Production of incomplete or not ignited hydrocarbons, like CO is the result of ignition air lacks. HC production source is the part of engine that the ignition flame doesn't exist. The gap between cylinder wall and the gaps were the flame can't penetrate is effective in HC pollutions.
Comparison of NO x emissions from biodiesel and diesel fuels 1600 1400 (ppm) NOx 1200 1000 800 600 400 200 B20D80 B10D90 B5D95 D100 0 1400 2000 1400 2000 R P M
Comparison of Smoke emissions from biodiesel and diesel fuels 350 Smoke (mg/m 3 ) 300 250 200 150 100 50 B20D80 B10D90 B5D95 D100 0 1400 2000 1400 2000 R P M
Comparison of Torque using biodiesel and diesel fuels 350 340 To orque (N.m m) 330 320 310 300 290 D100 B5D95 B10D90 B20D80 280 1400 2000 1400 2000 R P M
Comparison of Power emissions using biodiesel and diesel fuels 70 po ower (kw) 60 50 40 30 20 10 D100 B5D95 B10D90 B20D80 0 1400 2000 RPM
Because of more thermal efficiency and fuel consistency, biodiesel fuel have More torque and power efficiency than pure diesel fuels. It means that both the diesel and biodiesel compositions inter more fuel to combustion area, but because of more oxygen content t in biodiesel fuel, this fuels have more complete ignition and as result the torque and power of engine increase.
High deference in various periods is because of Air/Fuel portions. This portion in 2000 periods is AF=24.6 and in 1400 periods is AF=18. 3 (Testing engine has turbo charging system).
Summary Biodiesel is not toxic Biodiesel degrades four times faster than diesel Pure biodiesel degrades d 85-88 % in water Blending of biodiesel with diesel fuel increase engine efficiency. The higher flash point makes the storage safer. Biodiesel is an oxygenated fuel, thus implying that its oxygen content plays a role in making fatty compounds suitable as diesel fuel by cleaner burning.
90% reduction in cancer risks, according to Ames mutagenicity tests. Provides a domestic,renewable energy supply. Biodiesel does not produce greenhouse effects, because the balance between een the amount of CO 2 emissions and the amount of CO 2 absorbed by the plants producing vegetable oil is equal. Biodiesel can be used directly in compression ignition engines with no substantial modifications of the engine.
The emissions i of PAHs and npahs compounds revealed very lower levels biodiesel are compared to conventional diesel fuel. Chemical characteristics revealed very lower levels of some toxic and reactive hydrocarbon species when biodiesel fuels were used.
Recommendation As the stock of ffossil ilfuel lis getting depleted demphasis should be given to renewable sources of fuel such as biofuel: Design, develop and popularize appliances and equipments specifically for rural application. Prime facie, biodiesel seems to have significant potential to contribute to Iran s energy security, the need of the hour is to undertake R&D on sustainable plantation ti management, oil extraction ti and use environmental and social impact assessment and build institutional models. Contact training programs to sanitize media personnel on latest technologies and developments related to rural development. Creating awareness regarding loan, insurance facilities subsidies, et.
Final statement Why Bio diesel? Green fuel or fossil fuels? One Answer Cheaper fuel for consumers More energy security & diversified sources Higher farm incomes & rural employment Significant carbon emission reduction Faster GDP growth, Lower Imports & energy prices
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