Hanoi University of Technology School of Chemical Engineering Department of Organic & Petrochemical Technology

OVERVIEW OF BIODIESEL FUEL

Lecturer : Assoc.Prof.Dr. Nguyn Khnh Diu Hng Student: Nguyn L Ti Thu - KTHH1-K54

Contents
I. II. 1. 2. 3. III. 1. 2. IV. 1. 2. V. 1. 2. 3. 4. Introduction .............................................................................................................................. 3 Raw Materials for Biodiesel Production ............................................................................ 4 The first generation ................................................................................................................ 4 The second generation............................................................................................................ 6 The third generation ............................................................................................................... 7 Advantages and Disadvantages of Biodiesel ...................................................................... 8 Advantage .............................................................................................................................. 8 Disadvantages ........................................................................................................................ 8 Biodiesel and Biodiesel Standard ........................................................................................ 9 Biodiesel (B100) .................................................................................................................... 9 Biodiesel Blends .................................................................................................................. 17 Current Technologies in Biodiesel Production .................................................................... 19 Biodiesel production with batch processing......................................................................... 21 Production of biodiesel using a continuous gas-liquid reactor............................................ 22 Continuous process using a heterogeneous catalyst. ............................................................ 23 Biodiesel production with non-catalyzed transesterification ............................................... 25

I.

Introduction
If we analyze the worlds per capita energy consumption from 1980 to 2006, we will note that it was 63.7 million Btu in 1980, 66.0 million Btu is 1990 and in 2006, it jumped to 72.4 million Btu. The reasons of increase in the consumption may be population increase, massive industrialization or the increasing number of developing countries or there may be some other reasons. Fossil fuels are naturally occurring carbon or hydrocarbon fuel, such as coal, petroleum, peat, and natural gas, formed by the decomposition of prehistoric organisms. There are three major forms of fossil fuels: coal, oil and natural gas. These fossil fuels, though a few of them have been derived and made usable by civilizations in recent era but fossil fuels like coal, peat etc. have been in mans use since centuries. Then came the industrial era in which fossil fuels have been a widely used source of energy. Industrial development and technological advancements in this regard, all of these have their roots in the usage of these fossil fuels like oil, gas and coal etc Liquid biofuels are attracting increasing interest worldwide. Industrial countries see biofuels as a way of reducing Greenhouse Gas (GHG) emissions from the transport sector, while developing countries see biofuels as a way to stimulate rural development, create jobs, and save foreign exchange. Recent surges in the world oil price have prompted a wide range of countries to consider biofuels programmes. Modern biofuels (and bioenergy in general) have the potential to reduce the carbon intensity of development and could come to play an interesting role in supplementing the energy supply mix in both developed and developing countries. In many countries, developing as well as industrialised, bioenergy (of which biofuels are a subset) has become a centrepiece of renewable energy plans and policies because of its many practical, social and economic advantages. More fundamentally, modern bioenergy is now widely regarded as an important player in the global transition to a low carbon energy future which is needed to reduce human induced climate change. Experts suggest that current oil and gas reserves would suffice to last only a few more decades. To meet the rising energy demand and replace reducing

petroleum reserves, fuels such as biodiesel and bioethanol are in the forefront of alternative technologies. Accordingly, the viable alternative for compression-ignition engines is biodiesel. Biodiesel is defined as the mono alkyl esters of vegetable oils or animal fats. Biodiesel is the best candidate for diesel fuels in diesel engines. Biodiesel burns like petroleum diesel as it involves regulated pollutants. On the other hand, biodiesel probably has better efficiency than gasoline. Biodiesel also exhibits great potential for compression-ignition engines.

II.

Raw Materials for Biodiesel Production

1. The first generation The first generation of raw materials for biodiesel production are vegetable oils, animal fats and short chain alcohols. The oils most used for worldwide biodiesel production are rape-seed (mainly in the European Union countries), soybean (Argentina and the United States of America), palm (Asian and Central American countries) and sunflower, although other oils are also used, including peanut, linseed, safflower, used vegetable oils, and also animal fats. Since cost is the main concern in biodiesel production and trading (mainly due to oil prices), the use of non-edible vegetable oils has been studied for several years with good results. Besides its lower cost, another undeniable advantage of non-edible oils for biodiesel production lies in the fact that no foodstuffs are spent to produce fuel. These and other reasons have led to medium and large scale biodiesel production trials in several countries, using non-edible oils such as castor oil, tung, cotton, jojoba and jatropha. Animal fats are also an interesting option, especially in countries with plenty of livestock resources, although it is necessary to carry out preliminary treatment since they are solid; furthermore, highly acidic grease from cattle, pork, poultry, and fish can be used. Rapeseed: It is the most important raw material for biodiesel production in the European Community. However, there were technological limitations for

sowing and har-vesting in some Central and South American countries, mainly due to the lack ofadequate information about fertilization, seed handling, and storage. Moreover, low prices in comparison to wheat and low productionper unit area have limited its use. Soybean: It is a legume originating in East Asia. Depending on environmental conditionsand genetic varieties, the plants show wide variations in height. Leading soybean producing countries are the United States, Brazil, Argentina, China, and India. Biodiesel production form soybean yields other valuable sub-products in addition to glycerin: soybean meal and pellets (used as food for livestock) and flour (which have a high content of lecithin, a protein). Grain yield varies between 2,000 and 4,000 kg/hectare. Since the seeds are very rich in protein, oil content is around 18%. Oil Palm: Oil palm is a tropical plant that reaches a height of 2025 m with a life cycle of about 25 years. Full production is reached 8 years after planting. Two kinds of oil are obtained from the fruit: palm oil proper, from the pulp, and palm kernel oil, from the nut of the fruit (after oil extraction, palm kernel cake is used as livestock food). Several high oil-yield varieties have been developed. Indonesia and Malaysia are the leading producers. Sunflower: The great importance of sunflower lies in the excellent quality of the edible oil extracted from its seeds. It is highly regarded from the point of view of nutritional quality, taste and flavor. Moreover, after oil extraction, the remaining cake is used as a livestock feed. It must be noted that sunflower oil has a very low content of linoleic acid, and therefore it may be stored for long periods. Oil yield of current hybrids is in the range 4852%. Flax: Flax is a plant of temperate climates, with blue flowers. Flax seeds contain between 30 and 48% of oil, and protein content is between 20 and 30%. It is important to remark that linseed oil is rich in polyunsaturated fatty acids, linolenic acid being from 40 to 68% of the total. Castor Seed: Castor oil is a triglyceride, ricinolenic acid being the main constituent (about 90%). The oil is non-edible and toxic owing to the

presence of 15% of ricin, a toxic protein that can be removed by cold pressing and filtering. The presence of hydroxyl groups in its molecules makes it unusually polar as compared to other vegetable oils. Cotton: Among non-foodstuffs, cotton is the most widely traded commodity. It is produced in more than 80 countries and distributed worldwide. Cotton oil and flour are obtained from the seed. Jatropha: Jatropha is a shrub that adapts well to arid environments.Jatropha curcasis the most known variety; it requires little water or additional care; therefore, it is adequate for warm regions with little fertility. Productivity may be reduced by irregular rainfall or strong winds during the flowering season. Yield depends on climate, soil, rainfall and treatment during sowing and harvesting. Jatropha plants become productive after 3 or 4 years, and their lifespan is about 50 years. Oil yield depends on the method of extraction; it is 2832% using presses and up to 52% by solvent extraction. Since the seeds are toxic, jatropha oil is non-edible. The toxicity is due to the presence of curcasin (a globulin) and jatrophic acid (as toxic as ricin). Avocado: Oil may be obtained from the fruit pulp and pit. It has a high nutritional value, since it contains essential fatty acids, minerals, protein and vitamins A, B6, C, D, and E. The content of saturated fatty acids in the pulp of the fruit and in the oil is low; on the contrary, it is very high in monounsaturated fatty acids (about 96% being oleic acid). The oil content of the fruit is in the range 1230%. 2. The second generation Use of neat (unprocessed) vegetable oils in the compression ignition engines is reported to cause several problems due to its high viscosity. Biodiesel which is accepted as an attractive alternative fuel, is prepared by transesterification of vegetable oils and animal fats with an alcohol in presence of a catalyst. However, the land use for production of edible oil for biodiesel feedstock competes with the use of land for food production. Moreover, the price of edible plant and vegetable oils is usually higher than petro diesel. The use of waste cooking oil as biodiesel feedstock reduces the cost of biodiesel production since the feedstock costs constitutes

approximately 70-95% of the overall cost of biodiesel production. Hence, the use of waste cooking oils and non-edible oils should be given higher priority over the edible oils as biodiesel feedstock. Huge quantities of waste cooking oils and animal fats are available throughout the world, especially in the developed countries. Management of such oils and fats pose a significant challenge because of their disposal problems and possible contamination of the water and land resources. The Energy Information Administration in the United States estimated that some 100 million gallons of waste cooking oil is produced per day in USA. The total waste cooking oil produced in Canada could be approximately 135,000 tons/year. In the EU countries, the total waste cooking oil production was approximately 700,000-1,000,000 tons/yr. The UK produces over 200,000 tons of waste cooking oil per year. The use of waste cooking oil as a biodiesel source has a potential to reduce CO2, particulate matter and other greenhouse gases as the carbon contained in biomass-derived fuel is largely biogenic and renewable. Waste cooking oil, which is otherwise wasted, is one of the most economical choices to produce biodiesel. Since one of the major concerns on biodiesel production is the price of feedstock, utilization of waste cooking oil significantly enhances the economic viability of biodiesel production. 3. The third generation Microalgae appear to be a very important alternative for future biodiesel production due to their very high oil yield; however, it must be taken into account that only some species are useful for biofuel production. Microalgae have great potential for biodiesel production, since the oil yield (in liters per hectare) could be one to two orders of magnitude higher than that of other raw materials. Oil content is usually from 20 to 50%, although in some species it can be higher than 70%. However, it is important to note that not all microalgae are adequate for biodiesel production. High levels of CO2, water, light, nutrients and mineral salts are necessary for the growth of microalgae. Production processes take place in raceway ponds and photobiological reactors.

III.

Advantages and Disadvantages of Biodiesel

1. Advantage Cost: Biofuels have the potential to be significantly less expensive than gasoline and other fossil fuels. This is particularly true as worldwide demand for oil increases, oil supplies dwindle, and more sources of biofuels become apparent. Source material: Whereas oil is a limited resource that comes from specific materials, biofuels can be manufactured from a wide range of materials including crop waste, manure, and other by products. This makes it an efficient step in recycling. Renewability: It takes a very long time for fossil fuels to be produced, but biofuels are much more easily renewable as new crops are grown and waste material is collected. Security: Biofuels can be produced locally, which decreases the nation's dependence upon foreign energy. By reducing dependence on foreign fuel sources, countries can protect the integrity of their energy resources and make them safe from outside influences. Economic stimulation: Because biofuels are produced locally, biofuel manufacturing plants can employ hundreds or thousands of workers, creating new jobs in rural areas. Biofuel production will also increase the demand for suitable biofuel crops, providing economic stimulation to the agriculture industry. Lower carbon emissions: When biofuels are burned, they produce significantly less carbon output and fewer toxins, making them a safer alternative to preserve atmospheric quality and lower air pollution.

2. Disadvantages Energy output: Biofuels have a lower energy output than traditional fuels and therefore require greater quantities to be consumed in order to produce the same energy level. This has led some noted energy analysts to believe that biofuels are not worth the work.

 Production carbon emissions: Several studies have been conducted to analyze the carbon footprint of biofuels, and while they may be cleaner to burn, there are strong indications that the process to produce the fuel including the machinery necessary to cultivate the crops and the plants to produce the fuel - has hefty carbon emissions. High cost: To refine biofuels to more efficient energy outputs, and to build the necessary manufacturing plants to increase biofuel quantities, a high initial investment is often required. Food prices: As demand for food crops such as corn grows for biofuel production, it could also raise prices for necessary staple food crops. Food shortages: There is concern that using valuable cropland to grow fuel crops could have an impact on the cost of food and could possibly lead to food shortages. Water use: Massive quantities of water are required for proper irrigation of biofuel crops as well as to manufacture the fuel, which could strain local and regional water resources.

IV.

Biodiesel and Biodiesel Standard

1. Biodiesel (B100) This section describes the basic considerations for handling and blending B100. In the United States it is equally common to handle B99 and B99.9 blends, as these qualify for a federal blenders tax credit. The considerations in this section also apply to B99 and B99.9. The storage and handling procedures for B100 are very different from those for B20 and lower biodiesel blends, and they vary significantly from those of diesel fuel. Following are several significant attributes specific to B100 that should be considered when handling, storing,and using it. B100 is a good solvent. It may loosen or dissolve varnish and sediments in fuel tanks and fueling systems left by conventional diesel over time. If your system contains sediments, you should definitely clean your tanks and fuel system before handling or using B100.

 B100 freezes at higher temperatures than most diesel fuel. This must be taken into account if handling or using B100, especially in aboveground storage tanks. Most B100 starts to cloud at 35 to 60F (2 to 15C),so heated fuel lines and tanks may be needed, even in moderate climates, during winter. As B100 begins to gel, the viscosity also begins to rise to much higher levels than most diesel fuel does, which can increase the stress on pumps. The high cloud point makes B100 use challenging in colder climates. B100 is not compatible with some hoses and gaskets. B100 may soften and degrade certain types of rubber compounds used for hoses and gaskets (buna-N, nitrile, natural rubber) and may cause them to leak and degrade to the point where they crumble and become useless. For bulk handling of B100, seals, gaskets, and hoses must be compatible with B100. Using B100 in an engine constructed with incompatible materials can cause a fuel spill on a hot engine, ruin a fuel pump, or clog a filter as the hose material gradually erodes. Use extreme care to ensure any part of the fuel system that touches the fuel is compatible with B100. Some systems already have biodiesel-resistant materi-als, but many do not, because these materials are usually slightly more expensive. B100 is not compatible with some metals and plastics. Biodiesel will degrade and form high sediment levels if contacted for long periods by copper or copper containing metals (brass, bronze) or with lead, tin, or zinc (galvanized surfaces). These high sediment levels may clog filters. B100 may also permeate some common plastics (polyethylene, polypropylene) over time, so these s. hould not be used for storing B100. The ASTM specification for biodiesel (B100) is ASTM D6751. This specification is frequently updated, and this version is D6751-08a (2008):

Table1: Requirements for B100 Blend Stock as listed in ASTM D6751-08a (2008)

a. Carbon residue shall be run on the 100% sample. b. Atmospheric equivalent temperature. c. B100 intended for blending into diesel fuel that is expected to give satisfactory vehicle performance at fuel temperatures at or below 10F shall comply with a cold soak filterability limit of 200 s maximum. High levels of Group I and II metals: Sodium (Na), potassium (K), calcium (Ca), and magnesium (Mg) can cause deposits to form, catalyze undesired

side reactions, and poison emission control equipment. The Group I and II metals are limited as the combination of metals in each category, Na+K and Ca+Mg. For each combination, the limit is 5 ppm. Flash point: A minimum flash point for diesel fuel is required for fire safety. B100s flash point is required to be at least 93C (200F) to ensure it is classified as nonhazardous under the National Fire Protection Asso-ciation (NFPA) code. Alcohol: It is critical to ensure that the manufacturer has removed excess methanol used in the manufactur-ing process. Residual methanol in the fuel is a safety issue, because even very small amounts reduce the flash point; can affect fuel pumps, seals, and elastomers; and can result in poor combustion properties. The intent of the alcohol control requirement is to limit methanol to less than 0.2 wt %. This can be accom-plished by meeting a higher flash point requirement of 130C (266F); or by measuring methanol content by gas chromatography. Water and sediment: This refers to free water droplets and sediment

particles. The allowable level for B100 is set at the same level allowed for conventional diesel fuel. Poor drying techniques during manufacturing or contact with excessive water during transport or storage can cause B100 to be out of specification for water content. Excess water can lead to corrosion and provides an environment for microorganisms. Fuel oxida-tion can also raise sediment levels, so this test can be used in conjunction with acid number and viscosity to determine if fuels have oxidized too much during storage. Viscosity. A minimum viscosity is required for some engines because of the potential for power loss caused by injection pump and injector leakage. This is not an issue for B100, and the minimum is set at the same level as for petroleum diesel. Higher viscosity fuels can cause poor fuel combustion that leads to deposit formation as well as higher in cylinder penetration of the fuel spray, which can result in elevated engine oil dilution with fuel. The maximum allowable viscosity in ASTM D975 for No. 2 diesel is 4.1 mm2/s at 104F (40C). ASTM D6751 allows for slightly higher viscosity than

D975, primarily because that is where the normal viscosity of B100 lies. Biodiesel blends of 20 vol % or lower should have a viscosity within the range allowed by D975. Sulfated ash test: This test measures the amount of residual alkali catalyst in the biodiesel as well as any other ash-forming compounds that could contribute to injector deposits or fuel system fouling. Sulfur: This is limited to reduce sulfate and sulfuric acid pollutant

emissions and to protect exhaust cata-lyst systems when they are deployed on diesel engines in the future. Sulfur content of 15 ppm or lower is also required for proper functioning of diesel particle filters. Biodiesel generally contains less than 15 ppm sulfur. The test for low-sulfur fuel (ASTM D5453) should be used for accurate results instead of D2622, which will provide falsely high results caused by the tests interference with the oxygen in the biodiesel. Copper strip corrosion test: This test is used to indicate potential

difficulties with copper and bronze fuel system components. The requirements for B100 and conventional diesel are identical, and biodiesel meeting other D6751 specifications always passes this test. Cetane number: An adequate cetane number is required for good engine performance. Conventional diesel must have a cetane number of at least 40 in the United States. Higher cetane numbers help ensure good cold start properties and minimize the formation of white smoke. The ASTM limit for B100 cetane number is set at 47, because this is the level identified for Premium Diesel Fuel by the National Conference of Weights and Measures. Also, 47 has been the lowest cetane number found in U.S. biodiesel fuels. However, The cetane index (ASTM D976) is not an accurate predictor of cetane number for biodiesel or biodiesel blends, because it is based on a calculation that uses specific gravity and distillation curve, both of which are different for biodie-sel than for petroleum diesel. Cloud point: This is the most commonly used measure of low-temperature operability; fuels are generally expected to operate at temperatures as low as their cloud point. The B100 cloud point is typically higher than the cloud

point of conventional diesel. Cloud point must be reported to indicate biodiesels effect on the final blend cloud point. Carbon residue: This measures the carbon-depositing tendency of a fuel and is an approximation of the ten-dency for carbon deposits to form in an engine. For conventional diesel fuel, the carbon residue is measured on the 10% distillation residue. Because B100 boils entirely at the high end of the diesel fuel range and in a very narrow temperature range, it is difficult to leave only a 10% residual when distilling biodiesel. So, bio-diesel carbon residue specifies that the entire biodiesel sample be used rather than the 10% distilled residue. Acid number.The acid number for biodiesel is primarily an indicator of free fatty acids (natural degradation products of fats and oils) and can be elevated if a fuel is not properly manufactured or has undergone oxida-tive degradation. Acid numbers higher than 0.50 have been associated with fuel system deposits and reduced life of fuel pumps and filters. Free and total glycerin.These numbers measure the amount of unconverted or partially converted fats and by-product glycerin in the fuel. Incomplete conversion of the fats and oils into biodiesel can lead to high total glycerin. Incomplete removal of glycerin can lead to high free glycerin and total glycerin. If these numbers are too high, the storage tank, fuel system, and engine can be contaminated. Fuels that exceed these limits are highly likely to plug filters and cause other problems. One of the major shortcomings of the D6584 gas chromatograph (GC) method is its sensitivity to diesel fuel. Diesel fuel components react dif-ferently on the column used in the GC they make the determination of free glycerin very difficult and may damage the column. Thus, many labs are unable to determine free and total glycerin by this method in samples with even small amounts of diesel fuel, such as B99.9. Phosphorus content.This is limited to 10 ppm maximum in biodiesel

because it can damage catalytic con-verters; phosphorus above 10 ppm can be present in some plant oils. Biodiesel produced in the United States generally has phosphorus levels of about 1 ppm.

 T90 distillation specification: This specification was incorporated to ensure that fuels have not been contami-nated with high boiling materials such as used motor oil. B100 exhibits a boiling point rather than a distilla-tion curve. The fatty acids from which biodiesel are produced are mainly straight-chain HCs with 16 to 18 carbons that have similar boiling point temperatures. The atmospheric boiling point of biodiesel is generally 626 to 675F (330 to 357C). Oxidation stability.Biodiesel can oxidize during storage and handling, leading to the formation of peroxides, acids, gums, and deposits. The minimum oxidation stability requirement is intended to ensure the storage stability of B100 and biodiesel blends. Cold soak filterability: It was added in 2008 in response to data indicating that some B100 could, in blends with petroleum diesel of up to 20%, form precipitates above the cloud point. B100 meeting the cold soak filterability requirements does not form these precipitates. This, along with cloud point, is needed to predict low-temperature operability. The European standard EN 14214, supersedesthe biodiesel standards in European countries that are members of the European Committee for Standardization (CEN). Therefore, no standards from individual European countries are given. The European standard EN 14214 contains a separate section for low-temperature properties. The total temperature range for these CFPP classes is from +5C to 44C. Because the requirements regarding low-temperature properties vary, the standard ASTM D6751 has a report requirement for its cloud point parameter.

Table 2: EN 14214 (Europe): Automotive Fuels: FAME for Diesel Engine (2008)

2. Biodiesel Blends

2.1.

B5 and Lower Blends

The specification for conventional diesel fuel, ASTM D975, allows up to 5 vol % biodiesel to be blended into compliant diesel fuels. The biodiesel must meet D6751. The biodiesel blend must meet all the numeric require-ments for diesel fuel properties specified in D975; none were changed or relaxed to accommodate biodiesel. ASTM Method D7371 Standard Test Method for Determination of Biodiesel Fatty Acid Methyl Esters) Content in Diesel Fuel Oil Using Mid Infrared Spectroscopy (FTIR-ATR-PLS Method) must be used to determine the biodiesel blend percentage.

2.2.

B6 to B20 Blends

A new ASTM specification (D7467) was recently published for blends containing 6 vol % to 20 vol % biodiesel. The biodiesel must meet D6751. The requirements of this new specification are shown in Table 3. The requirements are based on those in D975, with some additions. The 90% distillation temperature is allowed to be 5C higher than that for D975 diesel fuel. New requirements for acid number, biodiesel content, and oxidation stability are included. The specification is designed such that if a D6751compliant B100 and a D975 compliant diesel fuel are blended, the resultant blend will meet the specification. However, diesel fuel that does not meet D975 can also be used, and biodiesel can be used to blend these properties into compliance.

Table 3: ASTM D7467 Specification For Diesel Blends B6 to B20 (2010)

V.

Current Technologies in Biodiesel Production

Of the several methods available for producing biodiesel, transesterification of natural oils and fats is currently the method of choice. The purpose of the process is to lower the viscosity of the oil or fat. Transesterification is basically a sequential reaction. Triglycerides are first reduced to diglycerides, which are subsequently reduced to monoglycerides, which are finally reduced to fatty acid esters. The order of the reaction changes with the reaction conditions. The main factors affecting transesterification are the molar ratio of glycerides to alcohol, catalysts, reaction temperature and time, and free fatty acid and water content in oils and fats. Transesterification is extremely important for biodiesel. Biodiesel as it is defined today is obtained by transesterifying triglycerides with methanol. Methanol is the preferred alcohol for obtaining biodiesel because it is the cheapest alcohol. Methanol is made to reactwith triglycerides to produce methyl esters (biodiesel) and glycerol. C3H5(OOCR)3 + 3CH3OH 3RCOOCH3 + C3H5(OH)3 The production processes for biodiesel are well known. There are four basic routes to biodiesel production from oils and fats: Base-catalyzed transesterification Direct acid-catalyzed transesterification Conversion of the oil into its fatty acids and then into biodiesel Non-catalytic transesterification of oils and fats Biodiesel produced by transesterification reactions can be alkali catalyzed, acid catalyzed, or enzyme catalyzed, but the first two types have received more attetion because of the short reaction times and low cost compared with the third one. Most of the biodiesel produced today is made with the basecatalyzed reaction for several reasons: It involves low temperature and pressure. It yields high conversion (98%) with minimal side reactions and reaction time. It allows a direct conversion into biodiesel with no intermediate compounds.

 It requires simple construction materials. Figure 1 shows the flow diagram of base-catalyzed biodiesel processing. The base-catalyzed production of biodiesel generally occurs using the following steps: Mixing of alcohol and catalyst Transesterification reaction Separation Biodiesel washing Alcohol removal Glycerine neutralization Product quality

Figure 1: Simplified flow diagram of base-catalyzed biodiesel processing

1. Biodiesel production with batch processing The simplest method for producing alcohol esters is to use a batch, stirred tank reactor. Alcohol-to-triglyceride ratios from 4:1 to 20:1 (mole:mole) have been reported, with a 6:1 ratio most common. The reactor may be sealed or equipped with a reflux condenser. The operating temperature is usually about 340 K, although temperatures from 298 K to 358 K have been reported. The most commonly used catalyst is sodium hydroxide, though potassium hydroxide also used. Typical catalyst loadings range from 0.3% to about 1.5%. Transesterification completion rates of 85 to 95% have been reported. Higher temperatures and higher alcohol to oil ratios can also enhance the completion rate. Typical reaction times range from 20 min to more than 1 h.
Warm Alcohol Water Biodiesel Water Separator Alcohol Waste Water Warm Water

Oil Methanol Catalyst

Stirred Tank Glycerin

Figure 2: Batch Processing In transesterification the oil is first added to the system, followed by the catacxlyst and methanol. The system is agitated during the reaction time. Then agitation is stopped. The alcohol is removed from both the glycerol and ester stream using an evaporator or a flash unit. The esters are neutralized, washed gently using warm, slightly acidic water to remove residual methanol and salts, and then dried. The finished biodiesel is then transferred to storage. The glycerol stream is neutralized and washed with soft water. The glycerol is then sent to the glycerol refining unit.

2. Production of biodiesel using a continuous gas-liquid reactor 2.1 Material Soya bean oil, beef tallow and methanol were used in this research as the feedstock while sodium methoxide or sodium hydroxide was used as catalysts. Beef tallow was supplied by PVL Proteins Ltd and Bakels Edible Oils (NZ) Ltd. Technical grade methanol was used as the alcohol source in all experiments. It was purchased from Ajax Fine Chemicals Ltd. The methanol was premixed with sodium hydroxide in the range of 0-10 g NaOH/ L methanol before being pumped into the reactor. Pre-mixing the sodium hydroxide with methanol allows the formation of sodium methoxide needed to catalyse the reaction. In some of the experiments, pure sodium methoxide was used as catalyst. Sodium hydroxide pellets, 99.98% and Sodium Methoxide 95% reagent grade were purchased from Sigma-Aldrich Co. 2.2 Equipment and process It was identified that diesel injection pump would be a suitable unit for generating small micro sized droplets of high surface area. The surface area generated in this process is an order of magnitude higher than the contact area in any standard mixing processes currently employed in biodiesel

processes based on liquid-liquid reaction. This simplified the geometry of the unit and allowed the reaction to be carried out in a spray like reactor unit. Methanol circulation as illustrated in Figure 3 was also a key design parameter. The reaction is carried out in a 2 m high x 0.38m diameter stainless steel tank as shown in Figure 3. The oil atomization is carried out using a high pressure diesel injection pump while methanol is pumped using a peristaltic pump. The process operates by injecting oil and fat through a high pressure nozzle into a reactor filled with methanol vapour carrying the catalyst and moving in counter current flow direction. This allows direct contact between the two phases with large contact area thereby promoting more heat and mass transfer. The high pressure nozzles in the system atomize the oil into small

droplets in the range of 100 to 200m diameter, thus significantly increasing the contact surface area of the methanol/oil.

Figure 3: Process Flow Diagram The desired reaction temperature is achieved by heating the reactor using a steam jacket and preheating the reactants before being fed to the reactor. Since the process operates at temperatures well above the alcohol boiling point, a higher rate of reaction was achieved. This process can operate at any temperature below the degradation temperature of fat and oil ( 200oC). To increase the reaction rate, a high methanol to oil ratio was used as in any other transesterifcation process. To improve reaction rate the reactants were pre-heated using a combination of steam and electrical heating. The oil was injected into the reactor at 100- 120oC while methanol was injected at 85-95 oC. This laboratory reactor was not designed as a pressure vessel and hence was heated using saturated steam of 1 bar. This limited the operating temperature to a maximum of 100oC. Based on this technology and with suitable method of heating, industrial reactors temperature below the degradation temperature of oil. 3. Continuous process using a heterogeneous catalyst. The catalyst section includes two fixed bed reactors that are fed by oil and methanol at a given ratio. Excess methanol is removed after each of the two may operate at any

reactors by a partial flash. Esters and glycerol are then separated in a settler. Glycerol phases are joined and the last traces of methanol are removed by vaporization. Biodiesel is recovered after final recovery of methanol by vaporization under vacuum and then purified to remove the last traces of glycerol. In this heterogeneous process, the catalyst is very stable with no metal leaching. There is no formation of either glycerate salts or metal soaps which affords the following advantages : no neutralization step is required, there is no introduction of water, and there is no salt formation; this accounts for an exceptional glycerol purity. In addition, there is no waste production of low-value fatty acids.

Figure 4: General scheme for a continuous heterogeneous catalyzed process The purity of methyl esters exceeds 99% with yields close to 100% of the theoretical. Glycerol treatment is much easier than in homogeneous catalyzed processes. A simple elimination of methanol by vaporization

suffices and no chemicals are required. The glycerol produced is neutral, clear and exempt from any salt, with purities above 98%. This valuable product could be used in many chemical applications without further treatment. If required, pharmaceutical grade can easily be reached. The process feeds are limited to vegetable oils and methanol and the only products are biodiesel and a high-purity glycerol that is free of water and salt. With all its features, the process can be considered as a green process. Experiments on methanolysis withacid containing vegetable oils have also been conducted with no special acid removal treatment of the raw material. Methanolysis of a blend of 5% oleic acid in rapeseed oil leads to an ester product composition compatible with biodiesel requirements. In that case, esterification and transesterification reactions occur simultaneously.

4. Biodiesel production with non-catalyzed transesterification There are two non-catalyzed transesterification processes. These are the BIOX process and the supercritical alcohol (methanol) process. 4.1 Biodiesel production with BIOX process The BIOX process is a new Canadian process developed originally by Professor David Boocock of the University of Toronto that has attracted considerable attention. Dr. Boocock has transformed the production process through the selection of inert cosolvents that generate an oil-richone-phase system. This reaction is over 99% complete in seconds at ambient temperatures, compared to previous processes that required several hours. BIOX is a technology development company that is a joint venture of the University of Toronto Innovations Foundation and Madison Ventures Ltd. Its process uses base catalyzed transesterification (specifically transmethylation) of fatty acids to produce methyl esters. It is a continuous process and is not feedstock specific. The unique feature of the BIOX process is that it uses inert reclaimable cosolvents in a single-pass reaction taking only seconds at ambient temperature and pressure. The developers are aiming to produce biodiesel

that is cost competitive with petrodiesel. The BIOX process handles not only grain-based feedstocks but also waste cooking greases and animal fats

Figure 5: BIOX cosolvent process The BIOX process uses a cosolvent, tetrahydrofuran, to solubilize the methanol. Cosolvent options are designed to overcome slow reaction times caused by the extremely low solubility of the alcohol in the triglyceride phase. The result is a fast reaction, on the order of 5 to 10 min, and no catalyst residues in either the ester or the glycerol phase. 4.2 Supercritical alcohol process Biodiesel fuel is one of the most promising bioenergies and can be produced from oils/fats through transesterification. A current commercial process for biodiesel production involves the use of alkali catalyst, followed by the removal of the catalyst and saponified products from free fatty acids. In addition, water containing waste oils/fats depress the catalyst activity. These cannot allow the low quality feedstocks, such as waste cooking oil and waste industrial oil, available for their efficient utilization. To overcome these problems, Saka and Kusdiana (2001) and Demirbas (2002) were the first to propose that biodiesel fuels may be prepared from

vegetable oils via non-catalytic transesterification withsupercritical methanol (SCM). A novel process of biodiesel fuel production has been developed by a non catalytic supercritical methanol method.

Figure 6: Supercritical transesterification process Supercritical methanol is believed to solve the problems associated with the two phase nature of normal methanol/oil mixtures by forming a single phase as a result of the lower value of the dielectric constant of methanol in the supercritical state. As a result, the reaction was found to be complete in a very short time. In contrast to catalytic processes under barometric pressure, the supercritical methanol process is non catalytic, involves much simpler purification of products, has a lower reaction time, is more environmentally friendly, and requires lower energy use. However, the reaction requires temperatures of 525 to 675 K and pressures of 35 to 60 MPa. Supercritical transesterification is carried out in a high pressure reactor (auto clave). In a typical run, the autoclave is charged with a given amount of vegetable oil and liquid methanol with changed molar ratios. The autoclave is supplied with heat from an external heater, and power is adjusted to give an

approximate heating time of 15 min. The temperature of the reaction vessel can be measured with an ironconstantan thermocouple and controlled at 5 K for 30 min. Transesterification occurs during the heating period. After each run, the gas is vented, and the autoclave is poured into a collecting vessel. The remaining contents are removed from the autoclave by washing with methanol. A method for non catalytic biodiesel production by supercritical methanol treatment (>512 K, >8.09 MPa) has been under development since 1998. Variables affecting the reaction were investigated followed by a proposal that the optimum conditions were 623 K, 20 MPa, and 9 min. Compared with the alkali catalyzed method, the supercritical methanol method has advantages in terms of reaction time and purification step.