Fatty acids ethyl esters from rice bran oil by in-situ esterification as a biodiesel fuel

Sevil Ozgl-Ycel* a , Selma Trkaya Istanbul Technical University, Chemical and Metallurgical Faculty, Chemical Engineering Department, 80626 Maslak- Istanbul, TURKEY Fax: 90 212 285 2925; yucels@itu.edu.tr

Fatty acids esters are known to be good alternative fuels(biodiesel). Due to the economic reasons, the use of cheap materials as substrats for biodiesel is being preferred. In this case, rice bran oil, which can not to be evaluated as an edible oil, is an interesting substrat. In-situ esterification of high-acidity rice bran oil with ethanol and sulfuric acid catalyst was investigated.The effects of free fatty acid (FFA) contents of rice bran oil and ethanol concentration on in-situ esterification were investigated and compositions of produced ethyl esters due to the conditions were determined. Research Objectives Fatty acid monoesters produced by esterification of fatty acids with monohydroxy compounds are fatty chemicals widely used in industry due to their lubricating and softening properties[1]. Additionally, methyl and ethyl esters of these fatty acids are recently being used in diesel fuels are renewable and clean energy sources. Producing ethyl ester rather than methyl ester is of considerable interest because it allows production of an entirely agricultural fuel, and the extra carbon brought by ethanol molecule slightly increases the heat and the cetane number?2?. However, because monoesters of vegetable oils are more expensive than corresponding petroleum products, cheaper raw materials are being searched. Therefore, in this study the use of rice bran oil, agricultural waste material that can not be evaluated as an edible oil in the country, in the production of ethyl esters was investigated. Rice bran which is obtained as a by-product in the milling of brown rice kernel to yield the familiar white rice, has an oil content that varies from 12 to 23 %, depending on variety of rice and degree of milling?3,4?. Oil extracted from bran may have low or high acidity, depending on the conditions and duration of storage. The rapid increase of free fatty acids (FFA) in the bran after milling has been recognized as a serious problem for rice bran industries. The principal cause of oil deterioration in the bran during storage is the activity of the lipase enzyme in the presence of moisture. For this reason only 6,5% world rice bran oil potential is evaluated as edible and the rest for industrial product purposes. In-situ Esterification Ethyl ester production carried out from fats and oils by alkaline-catalyzed interesterification(ethanolysis) or by direct esterification of inexpensive fatty acids using acidic catalyst. While the esterification of fatty acids is fast in acidic media, the fast esterification of triglicerides is performed in alkali media. So, the esterification of high-acidity oils such as rice bran oil, presents production problem due to their high contents of free fatty acids(FFA), mono- and diglicerides. For this reason, rapid and efficient conversion of high acidity oils to ethyl esters by onestep is not practical. In this study, the production of fatty acids monoesters of rice bran oil by in-situ esterificatio n method was investigated. In this method, the oil was not extracted from the seed and reacted with the alcohol with acid catalyst. The extraction and monoester production occured simultaneously. In-situ esterification method is preferred to conventional methods, not only one-step esterification of high acidity oils but also provides pure products[5,6,7]. Conclusion In this study, in-situ esterification of rice bran oil with ethanol(96%) was investigated using sulfuric acid. The effect of FFA content of rice bran oil and ethanol concentration on the yield and purity of obtained esters was investigated. The results showed that the ethyl ester content of products changed considerably with the FFA content of rice bran oil. The ester content of product increase from 36,6% to 78% with increasing the FFA content of oil from 14.5% to 81.0, respectively. Similarly, it was also observed that high amount of the esters products obtained from rice bran oils containing high FFA.

In the second part of the study, in-situ esterification experiments were conducted with 99.1% ethanol and these results were compared with 96% ethanol. It was seen that the increasing of ethanol concentration resulted in significant increasement in the yield of esters from low-acidity bran oils, i.e., the ester yield increased about 20% when the rice bran oil, having 14% FFA was treated with 99.1% ethanol. However, bran oils with high FFA contents used in the esterification reaction 99.1% ethanol did not effect practically the yield of ester. As a conclusion, production of ethyl esters from a cheap raw material such as rice bran oil by in-situ esterification method would increase the importance of these esters as a clean and alternative energy source. References ?1? Meffret A., Technical Uses of Fatty Acid Esters, J.Am.Oil Chem.Soc., 1984, 61, p.255-258. 427- 432. ?2? Fillieres L., Benjelloun-Mlayah, B. Delmas, M., Ethanolysis of Rapeseed Oil: Quantitation of Ethyl Esters, Mono-Di-, and Triglycerides and Glycerol by High-Performance Size-Exclusion Chromatography, J.Am.Oil Chem.Soc., 1995, 72, p.427- 432. ?3? Gupta,H.P., Rice Bran Offers in Indian Oil Source. J. Am. Oil Chem.Soc., 1989, 66, p. 620-623. ?4? Saunders R.M., Rice Bran Composition and Potential Food Uses, Food Reviews International, 1986, 1, p.465-495. ?5? Ozgl, S. Trkay, S., In-situ Esterification of Rice Bran Oil with Methanol and Ethanol, J.Am.Oil Chem.Soc., 1993, 70, p.145-147. ?6? Kildiran, G. Ycel, S.O.. Trkay, S., In-situ Acoholysis of Soybean Oil, J.Am.Oil Chem.Soc., 1996, 73, p.223-225. ?7? Harrington, K.J., D'Arcy-Evans, C., A Comparison of Conventional and In-Situ Methods of Transesterification of Seed Oil from a Series of Sunflower, J.Am.Oil Chem.Soc., 1985, 62, p.10091013.