BIODIESEL PRODUCTION AND FUEL QUALITY-REVIEW: PRODUCTION PROCESS FACTORS

Posted by Kathryn Schwartz on December 03, 2013
Trans-esterification

PROCESS FACTORS

The most important issue during biodiesel production is the completeness of the trans-esterification reaction. The basic chemical process that occurs during the reaction is indicated by the following sequence of events:
Biodiesel Production and-13

The triglycerides are converted to diglycerides, which in turn are converted to monoglycerides, and then to glycerol. Each step produces a molecule of a methyl ester of a fatty acid. If the reaction is incomplete, then there will be triglycerides, diglycerides, and monoglycerides left in the reaction mixture. Each of these compounds still contains a glycerol molecule that has not been released. The glycerol portion of these compounds is referred to as bound glycerol. When the bound glycerol is added to the free glycerol, the sum is known as the total glycerol. The ASTM specification requires that the total glycerol be less than 0.24% of the final biodiesel product as measured using a gas chromatographic method described in ASTM D 6584. Since the glycerol portion of the original oil is usually about 10.5%, this level of total glycerol corresponds to 97.7% reaction completion.

Other methods can be used to measure total glycerol such as a high performance liquid chromatography (HPLC; for example AOCS Recommended Practice Ca 14b-96: Quantification of Free Glycerine in Selected Glycerides and Fatty Acid Methyl Esters by HPLC with Laser Light-Scattering Detection) or a chemical procedure such as that described in AOCS Official Method Ca 14-56 (Total, Free and Combined Glycerol Iodometric Method). All of these techniques require a fairly high level of training and some laboratory equipment. Only the gas chromatographic procedure is acceptable for demonstrating compliance with ASTM D 6751.

Free glycerol

Free glycerol refers to the amount of glycerol that is left in the finished biodiesel. glycerol is essentially insoluble in biodiesel so almost all of the glycerol is easily removed by settling or centrifugation. Free glycerol may remain either as suspended droplets or as the very small amount that is dissolved in the biodiesel. Alcohols can act as co solvents to increase the solubility of glycerol in the biodiesel. Most of this glycerol should be removed during the water washing process.

Water-washed fuel is generally very low in free glycerol, especially if hot water is used for washing. Distilled biodiesel tends to have a greater problem with free glycerol due to glycerol carry-over during distillation. Fuel with excessive free glycerol will usually have a problem with glycerol settling out in storage tanks, creating a very viscous mixture that can plug fuel filters and cause combustion problems in the engine.

Residual Alcohol and Residual Catalyst

Since methanol (and ethanol) and the alkaline catalysts are more soluble in the polar glycerol phase, most will be removed when the glycerol is separated from the biodiesel. However, the biodiesel typically contains 2-4% methanol after the separation, which may constitute as much as 40% of the excess methanol from the reaction. Most processors will recover this methanol using a vacuum stripping process. Any methanol remaining after this stripping process should be removed by the water washing process.

Therefore, the residual alcohol level in the biodiesel should be very low. A specific value for the allowable alcohol level is specified in European biodiesel standards (0.2% in EN 14214), but is not included in the ASTM standard. Tests have shown that as little as 1% methanol in the biodiesel can lower the flashpoint of the biodiesel from 170°C to less than 40°C. Therefore, by including a flashpoint specification of 130°C, the ASTM standard limits the amount of alcohol to a very low level (<0.1%). Residual alcohol left in the biodiesel will generally be too small to negatively impact the fuel’s performance. However, lowering the flashpoint presents a potential safety hazard as the fuel may need to be treated more like gasoline, which also has a low flashpoint, than diesel fuel.

Most of the residual catalyst is removed with the glycerol. Like the alcohol, remaining catalyst should be removed during the water washing. Although a value for residual catalyst is not included in the ASTM standard, it will be limited by the specification on sulfated ash. Excessive ash in the fuel can lead to engine deposits and high abrasive wear levels. The European standard EN 14214 places limits on calcium and magnesium as well as the alkali metals sodium and potassium. From the statistical analysis it can be concluded that, within the experimental range, initial catalyst concentration is the most important factor on the transesterification process. It has a positive influence on the response; that is, ester yield increases with increasing catalyst concentration.

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