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Biodiesel Production
Biodiesel Production
Biodiesel production
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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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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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.
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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
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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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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