10 Biodiesel production

Jon Van Gerpen Department of Biological and Agricultural Engineering, 419 Engineering Physics Building, University of Idaho, P.O. Box 440904, Moscow (e-mail: jonvg@uidaho.edu)

1. Introduction
Biodiesel is a fuel for diesel engines that consists of the mono-alkyl esters of fatty acids from vegetable oils and animal fats. It can be used either pure, or in blends with petroleum-based diesel fuel. It does not require that engines or fueling infrastructure be modified although checking elastomers for compatibility is recommended when pure biodiesel (B100) is used. Biodiesel allows diesel engines to produce lower exhaust emissions of smoke, particulate, carbon monoxide, and unburned hydrocarbons. Oxides of nitrogen may increase slightly under some operating conditions but the difference for biodiesel blends up to 20% is difficult to measure. Biodiesel provides a major new market for excess supplies of vegetable oil and animal fats. The reduction in these excess supplies should improve prices for commodity oilseeds such as soybeans and canola. It could also encourage the development of greater diversity in crop production as oilseeds with greater oil yield per acre become economically viable. Biodiesel can also displace a portion of the petroleum used for transportation and, because it is biologically-based, may reduce the impact of global warming. However, its impact on these issues should not be exaggerated. Current world production of vegetable oils and animal fats and competition for these oils and fats from food uses will limit biodiesels contribution to less than 5% of petroleum diesel fuel for the foreseeable
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P. Ranalli (ed.), Improvement of Crop Plants for Industrial End Uses, 281289. 2007 Springer.

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future. So, while biodiesels impact on these problems is positive, it will be small. Biodiesel provides an improvement in diesel fuel lubricity, even when used in blends as low as 1 to 2%. This benefit is increasingly important as low-lubricity desulfurized diesel fuels are required. Recent work suggests that the actual lubricity benefit may be associated with contaminants in the biodiesel, such as free fatty acids and monoglycerides, rather than the mono-alkyl esters themselves (Knothe G. and Steidley KR 2005). The combination of high petroleum prices and government incentives has caused a surge in interest in biodiesel in the United States. Production capacity is increasing rapidly. This paper describes the processing technology that is being used to produce the fuel in the United States.

2. Oil preparation
Figure 10.1 shows a schematic diagram of the process to convert oilseeds to biodiesel. Oil is extracted from vegetable sources using hexane as a solvent, or with a mechanical screw press. A by-product of the oil extraction is meal, which in the case of soybeans and canola, is a high protein animal feed. For soybeans, the meal has higher value than the oil. The crude oil contains contaminants such as phospholipids, free fatty acids, and water that should be removed before converting the oil to biodiesel. The phospholipids, or gums, are removed by adding water to the oil while heating so the gums react with the water to form an insoluble sediment that can be removed by centrifugation, filtration, or settling and sold as crude lecithin. A fraction of the gums may require the addition of phosphoric acid to complete the hydration process so that all of the gums can be removed. Solvent-extracted soybean oil typically contains gum compounds equivalent to 900 ppm of phosphorus. Levels below 50 ppm are recommended for biodiesel production (Van Gerpen and Dvorak 2002). To remove free fatty acids from the oil, a solution of sodium hydroxide in water is added to convert the free fatty acids to soap. Then, the soap is washed from the oil with water and the oil is dried. The resulting material, known as soapstock, contains the soap, unseparated oil, and water.

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Fig. 10.1. Schematic diagram of Biodiesel production process.

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The by-products of oil refining, lecithin and soapstock, both have uses in the production of human and animal food products. In addition to the refining processes described above, oil that is being prepared for human consumption is generally bleached and deodorized (Erickson 1995; Zehnder 1995). However, these steps are unnecessary for biodiesel production. Some oils and fats contain high levels of free fatty acids. If these were processed using the caustic stripping process described above, the large amounts of soapstock would be a significant loss of useful product. The difficulty with leaving the free fatty acids in the oil for biodiesel production is that when the oil is subjected to the alkali-catalyzed transesterification process described below, the catalyst reacts quickly with the free fatty acids to form soap. This removes the catalyst from the reaction and the soap inhibits the biodiesel-glycerin separation process. If the level of free fatty acids is less than about 5%, the oil or fat may still be processed with an alkali catalyst. In this case, an amount of extra catalyst is added to compensate for that lost to reaction with the free fatty acids and which ensures sufficient catalyst will remain to catalyze the reaction. Above 5%, the amount of soap inhibits separation of the glycerin. When the free fatty acid level is above 5%, the excessive soap formation and the reduction in yield makes it necessary to use other means to process the feedstock. The most common method is to add a significant excess of methanol (commonly a 20:1 molar ratio of methanol to free fatty acids) with a strong acid, such as sulfuric acid (Canakci and Van Gerpen 2001). The acid catalyzes the esterification reaction of the fatty acids to methyl esters. When the level of free fatty acids has been reduced below 0.5%, the mixture can be passed through the transesterification process as if it were a refined oil. No soap is formed in the esterification reaction, but water is produced that must be removed before the mixture is transesterified or soap formation will be excessive.

3. Transesterification and separation

Transesterification is the process that takes a triglyceride molecule, itself an ester, and reacts it with an alcohol such as methanol to form the monoesters (biodiesel) and another alcohol (glycerol). This is an equilibrium reaction that stops well short of completion when the stoichiometric amount of methanol is added to the triglycerides. To force the equilibrium to the point where more than 98% of the glycerin has been separated from the triglycerides to produce biodiesel, at least 100% excess alcohol is required (Freedman and Pryde 1982). This degree of reaction is necessary to meet the biodiesel specification established by the American Society for Testing

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and Materials (ASTM). Incomplete reaction leaves excessive amounts of monoglycerides in the biodiesel. These partially reacted products have a low solubility in the biodiesel and the saturated monoglycerides will form crystals that appear as white flakes in the fuel. Once formed, the crystals can be difficult to re-dissolve, particularly after blending with diesel fuel. If present in sufficient quantity, these crystals can plug fuel filters. The most common alcohol used for transesterification is methanol, but ethanol can and has been used (Peterson et al. 1991). Ethanol requires more alcohol to be used and is usually more expensive. However, the extra weight of ethanol is converted to biodiesel so the higher cost of the ethanol may be offset by the greater yield. Both hydroxide and methoxide catalysts are commonly used to produce biodiesel. Sodium or potassium hydroxide are dissolved in methanol to produce methoxide ions, which are the actual catalytic agents. Unfortunately, hydroxide catalysts also produce water which results in hydroxyl ions. These hydroxyls provide a parallel reaction path that produces free fatty acids and soaps instead of the methyl esters which are sought. Most commercial biodiesel producers in the United States use sodium methoxide which is formed via a water-free process and is available in concentrated solutions of 25% or 30% in methanol. Solid-phase, or heterogeneous, catalysts are being developed for biodiesel production and will probably see widespread use in the next 2 to 3 years. The transesterification process can be conducted in a batch reactor where a typical reaction time is one hour at 60C. Continuously stirred tank reactors (CSTRs) are most commonly used in continuous plants. These operations usually use two CSTRs in series with approximately an hour of average residence time in each reactor. Glycerin separation between the two CSTRs helps to force the reaction equilibrium toward complete conversion of the triglycerides to methyl esters. The first reactor provides 75-90% of the reaction and the second reactor completes the process. Plug flow reactors can also be used but are less common due to the difficulty of providing sufficient reaction time. Glycerin separation can be accomplished by gravity with a decanter, with a centrifuge, or with coalescence technology. The glycerin produced will only be about 50% purity having attracted about half of the excess methanol and most of the catalyst and soaps. Refining of glycerin to the 99.5+% level required for most commercial glycerin applications is generally not done by biodiesel producers. It is more common to upgrade the glycerin to 80% purity, which will be accepted by commercial glycerin refiners. This upgrading is accomplished by acidulating the glycerin with a strong acid such as hydrochloric, sulfuric or phosphoric, to neutralize the catalyst and split the soaps. Since the free fatty acids produced by the soap splitting are not soluble in the glycerin, they can be removed and used for

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biodiesel production or introduced into animal feed. Then, the methanol is recovered from the glycerin by evaporation. This methanol may contain substantial amounts of water that must be removed, usually by fractional distillation, before the methanol can be returned to the reaction. After these processes, the glycerin will be 80 to 90% pure, depending on the contaminants in the original oil.

4. Methanol recovery and washing

After the biodiesel has been separated from the glycerin, it will contain small amounts of residual catalyst, soap, free glycerin and approximately 3 to 5% methanol. Excessive catalyst and soap will cause ash deposits in the engine and are controlled by the sulfated ash limitation in the ASTM specification. Free glycerin can cause filter plugging, injection system damage, and engine shutdown. Residual methanol causes a low flash point temperature and makes the fuel less safe to handle. These contaminants must be removed before the fuel will meet the ASTM specification used in the United States. There are two general approaches in common use to remove these impurities. In the approach depicted in Figure 10.1, the methanol is removed first by evaporation with either a flash or falling film evaporator. Then, the methanol-free biodiesel is washed with water. The water might be sprayed into the biodiesel, mixed with the biodiesel via bubble-induced agitation, or contacted in counterflow in a packed or agitated extraction column. Other variations involve adding acids such as citric or hydrochloric to the initial wash water to neutralize the catalyst and possibly split the soaps into free fatty acids and salts. The free fatty acids will remain in the fuel and the salts are easily removed with subsequent water washing. A flash drying process follows the last contact with water to ensure that residual water levels in the fuel are low. If the biodiesel is not dried in this manner it may appear cloudy due to the presence of small water droplets suspended in the fuel. In this case, it will generally become clear with time as the droplets settle to the bottom of the holding tank. An alternative process is to add wash water to the biodiesel immediately after the glycerin separation as shown in Figure 10.2. As before, acid is often added to the initial wash water for neutralization and soap splitting. Along with the soaps, salts, and free glycerin, most of the methanol will be transferred from the biodiesel to the wash water. The biodiesel is passed through a final flash vaporization process to ensure that any remaining methanol and water are removed.

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The first process, where methanol removal precedes water washing, has the advantage of providing methanol with a low water concentration. Since most of the water that may have entered the reaction as a contaminant in the oil or methanol will have been extracted with the glycerin after the first stage of reaction, the methanol removed from the biodiesel probably has a low enough water content to be returned to the reaction with no further processing. In contrast, the methanol recovered from the biodiesel with the second process will contain 50 to 90% water and requires separation by fractional distillation. However, the first process has the disadvantage that when the methanol is vaporized, if the soap concentration is too high, it will precipitate out as a viscous sludge. When present, the methanol acts as a co-solvent and holds the soap in solution. This precipitated soap can plug filters and screens and complicate the washing process.
From separation

Water

Washing Gray water + methanol

Methanol recovery and drying

To Additization

Fig. 10.2. Alternative washing process. The acidulation that starts the second process breaks up the soap and thus eliminates this precipitation problem. The second process also has the advantage that only one vaporization process is required (because the water/methanol separation as been deferred to the distillation column) while the first process requires separate methanol and water removal processes. The first process is probably more appropriate when processing clean refined oils with low water concentrations that will produce little soap. The

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second process is more robust for processes where higher soap levels are expected. With either process, gray water is produced. In addition to soaps, the water may contain methanol, free glycerin, salts, and catalyst. The water will have a high biological oxygen demand and would require neutralization and dilution before being sent to a waste water treatment plant. A more common option is to add the gray water stream to the crude glycerin. The acidulation of the glycerin will also split the soaps in the water and the water will be removed by the vaporization process that recovers the methanol. After distillation to separate the methanol and water, the methanol can be reused for the transesterification process and the water can be reused for washing. The salts remain in the glycerin. Alternatives to water washing are being proposed. Most involve adsorbents such as magnesium silicate or ion exchange resins. These materials are effective at removing soap, catalyst, free glycerin and, in some cases, monoglycerides. While the absorbents are costly and create a waste stream of spent absorbent, they allow considerable savings in water treatment costs and eliminate the challenges associated with emulsion formation during water washing.

5. Additization
Biodiesel properties may be enhanced by additives. In order to provide acceptable cold flow properties, biodiesel is generally produced from feedstocks that contain substantial amounts of unsaturated fatty acids. These compounds are prone to oxidative attack from oxygen in the atmosphere. Some feedstocks, such as soybean oil, contain potent natural antioxidants such as tocopherol that protect the fuel for six months or more. In cases where extended storage is expected, an antioxidant additive such as tertbutylhydroquinone (TBHQ) is used, frequently accompanied by a metal chelator such as citric acid. Pour point depressant additives are also available for biodiesel but these have only been found to be effective in blends of biodiesel with petroleum-based diesel fuel and are generally added after blending by the distributor or the consumer.

6. Conclusions
Biodiesel is an alternative fuel that is widely used in Europe and is attracting rapidly growing interest in the United States and other parts of the

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world. In the U.S., production capacity is increasing very rapidly due to federal government tax incentives and high petroleum prices. Production of biodiesel utilizes very well-known reaction and separation processes. Some variations exist between plants, but most of the processes are similar. While future developments, such as heterogeneous catalysts, will certainly make an impact, processing is likely to follow well-accepted procedures with increasing commonality between plants in a manner that is similar to that currently found in the fuel ethanol industry.

References
ASTM, Standard Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels. ASTM D 6751-02, American Society for Testing and Materials Canakci M, Van Gerpen J (2001) Biodiesel Production from Oils and Fats with High Free Fatty Acids, Transactions of the American Society of Agricultural Engineers vol 44 no. 6: pp 1429-1436 Erickson DR (1995) Bleaching/Adsorption Treatment. In: Erickson DR (ed) Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, IL Freedman B, Pryde EH (1982) Fatty Esters from Vegetable Oils for Use as a Diesel Fuel, from Vegetable Oil Fuels. In: Proceedings of the International Conference on Plant and Vegetable Oils as Fuels, ASAE, St. Joseph, MI Knothe G, Steidley KR (2005) Lubricity of Components of Biodiesel and Petrodiesel. The Origin of Biodiesel Lubricity. Energy and Fuels 19: pp 1192-1200 Peterson CL, Feldman M, Korus R, Auld DL (1991) Batch Type Transesterification Process for Winter Rape Oil. ASAE Transactions, vol 7 n.6: pp 711-716 Van Gerpen JH, Dvorak B (2002) The Effect of Phosphorus Level on the Total th Glycerol and Reaction Yield of Biodiesel. Bioenergy 2002. The 10 Biennial Bioenergy Conference, Boise, ID Zehnder CT (1995) Deodorization. In: Erickson DR (ed) Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, IL