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Esterification of High Concentration Free Fatty Acid in Rice Bran Oil

미강유 중 고농도 자유지방산의 에스테르화

  • Shin, Yong-Seop (Department of Civil and Environmental Engineering, Kyungsung University)
  • 신용섭 (경성대학교 건설환경공학부)
  • Published : 2008.02.28

Abstract

Characteristics of the esterification reaction between free fatty acid in rice bran oil and methanol was investigated in the presence of catalysts, such as PTS(p-toluene sulfonic acid), Amberlyst 15 dry and SCX(silica gel based strong cation exchange resin). While reaction temperature was kept constant at $65^{\circ}C$, initial feed content of free fatty acid was varied from 100% to 1% by addition of pure free fatty acid which was previously made from rice bran oil. Also, the effect of mole ratio of methanol to fatty acid on the final conversion was examined. When esterification of pure free fatty acid was catalyzed by several acids, final conversions were increased in order of Amberlyst 15 dry, SCX and PTS. Using PTS catalyst, initially the reaction proceeded in homogeneous 2nd oder reaction mechanism. However, phase of reaction mixture changed from homogeneous to heterogeneous along the reaction time and then reaction rate was retarded by mass transfer resistance of methanol. Final conversion of free fatty acid in reaction mixture was depended on initial feed content of free fatty acid, and had maximum value at 30% of initial feed free fatty acid content for all kinds of catalysts used. And the final conversion was increased with mole ratio of methanol by the improvement of reaction rate. When initial feed free fatty acid content below 10% and the reaction was catalyzed by PTS, concentration of free fatty acid in reaction mixture was increased in the middle of reaction time by hydrolysis of triglyceride in reaction mixture. Also, if silica gel was added into the reaction mixture which had initial feed free fatty acid content below 50%, final conversion was increased by the adsorption of moisture produced. The SCX catalyst made the esterification reaction of free fatty acid to progress like in case of PTS catalyst. However, when initial feed free fatty acid content below 10%, concentration of free fatty acid in. reaction mixture was decreased monotonically and not increased in the middle of reaction time on the contrary to the case of PTS. Thus, SCX catalyst accomplished more high value of final conversion than PTS catalyst for the initial feed fatty acid content range from 50% to 5% In case of initial feed free fatty acid content of 1% and mole ratio of methanol was 2, concentration of free fatty acid in reaction mixture increased over the initial feed free fatty acid content for all kind of catalysts used. Although SCX catalyst was added into reaction mixture which had 1% of initial feed fatty acid content, final conversion was hardly raised by mole ratio of methanol.

Keywords

References

  1. 이진석, 2000, 자동차 연료로서 바이오디젤유의 생산 및 이용현황, ETIS, 9, 1-10
  2. 오영택, 1996, 디젤기관 자동차의 대체연료로서 폐식용유의 이용, 에너지 절약기술웍샾, 11, 262-275
  3. Bartholomew D., 1981, Vegetable oil fuel, JAOCS, 58, 286A-288A https://doi.org/10.1007/BF02541575
  4. Ma F., Hanna M. A., 1999, Biodiesel production: a review, Bioresource Technology, 70, 1-15 https://doi.org/10.1016/S0960-8524(99)00025-5
  5. Tyson K. S., 2005, DOE analysis of fuels and coproducts from lipids, J. Fuel Processing Technology, 86, 1127-1136 https://doi.org/10.1016/j.fuproc.2004.11.007
  6. 이웅영, 2007, 바이오디젤, NICE, 25(5), 471-474
  7. Ceriani R., Meirelles A. J. A., 2006, Simulation of continuous physical refiners for edible oil deacidification, Journal of Food Engineering, 76, 261-271 https://doi.org/10.1016/j.jfoodeng.2005.05.026
  8. Rodrigues C. E. C., Onoyama M. M., Meirelles A. J. A., 2006, Optimization of the rice bran oil deacidification process by liquid-liquid extraction, ibid, 73, 370-378 https://doi.org/10.1016/j.jfoodeng.2005.02.004
  9. Gerpen J. V., 2005, Biodiesel processing and production, J. Fuel Processing Technology, 86, 1097-1107 https://doi.org/10.1016/j.fuproc.2004.11.005
  10. Meher L. C., Sagar D. V., Naik S. N., 2006, Technical aspects of biodiesel production by transesterification -a review, Renewable and Sustainable Energy Reviews, 10, 248-268 https://doi.org/10.1016/j.rser.2004.09.002
  11. Marchetti J. M., Miguel V. U., Errazu A. F., 2007, Possible methods for biodiesel production, ibid, 11, 1300-1311 https://doi.org/10.1016/j.rser.2005.08.006
  12. Berrios M., Siles J., Martin M. A., Martin A., 2007, A kinetic study of the esterification of free fatty acids in sunflower oil, Fuel, 86, 2283-2388 https://doi.org/10.1016/j.fuel.2007.01.036
  13. Hou X., Qi Y., Qiao X., Wang G., Qin Z., Wang J., 2007, Lewis acid catalyzed transesterification and esterification of high free fatty acid oil in subcritical methanol, 24(2), Korean J. Chem. Eng., 311-313 https://doi.org/10.1007/s11814-007-5052-x
  14. Chonghong S., Tongurai C., Chetpattananondh P., Bunyakan C., 2007, Biodiesel production by esterification of palm fatty acid distillate, Biomass and Bioenergy, 31, 563-568 https://doi.org/10.1016/j.biombioe.2007.03.001
  15. Takagaki A., Toda M., Okamura M., Kondo J. N., Hayashi S., Domen K., Hara M., 2006, Esterification of higher fatty acids by novel strong solid acid, Catalyst Today, 116, 157-161 https://doi.org/10.1016/j.cattod.2006.01.037
  16. Ni J., Meunier F. C., 2007, Esterification of free fatty acids in sunflower oil over solid acid catalysts using batch and fixed bed reactors, Applied Catalysis A: General, 333, 122-130 https://doi.org/10.1016/j.apcata.2007.09.019
  17. 이수곤, 채희정, 유정우, 김의용, 2006, 바이오디젤공정에서 이온교환수지 촉매에 의한 원료유의 전처리, 한국생물공학회지, 21(1), 68-71
  18. 정귀택, 박돈희, 2006, 고농도 유리지방산을 함유한 원료유의 전처리, ibid, 21(6), 418-421
  19. Diaz I., Alvarez C. M., Mohino F., Pariente J. P., Sastre E., 2000, Combined alkyl and sulfonic acid functionalization of MCM-41 type silica: part 2. esterification of glycerol with fatty acids, Journal of Catalysis, 193, 295-302 https://doi.org/10.1006/jcat.2000.2899
  20. Mbaraka I. K., Radu D. R., Lin V. S. Y., Shanks B. H., 2003, Organosulfonic acid functionalized mesoporous silicas for the esterification of fatty acid, ibid, 219, 329-336 https://doi.org/10.1016/S0021-9517(03)00193-3
  21. Mbaraka I. K., Shanks B. H., 2005, Design of multifunctionalized mesoporous silicas for esterification of fatty acid, ibid, 229, 365-373 https://doi.org/10.1016/j.jcat.2004.11.008
  22. 문성훈, 이준식, 1980, 유리지방산을 많이 함유한 미강유와 글리세린의 에스테르화 반응에 관한 연구, 한국식품과학회지, 12(3), 193-199
  23. Zullaikah S., Lai C., Vali S.R., Ju Y.,2005, A two-step acid catalyzed process for the production of biodiesel from rice bran oil. Bioresource Technology, 96, 1889-1896 https://doi.org/10.1016/j.biortech.2005.01.028
  24. Bak Y. C., Choi J. H., Kim S. B., Kang D. W., 1996, Production of biodiesel fuels by transesterification of rice bran oil, Korean J. Chem. Eng.,13(3), 242-245 https://doi.org/10.1007/BF02705945
  25. 김영주, 김덕근, 이영우, 박순철, 이진석, 2005, Amberlyst 15 촉매의 존재 하에서 올레산과 메탄올의 에스테르화 반응 속도식 연구, Korean Chem. Eng. Res., 43(5), 621-626