Abstract
An integrated biodiesel process that combines enzymatic esterification and alkaline transesterification is suggested. With focus on the enzymatic step, the paper provides proof of concept and suggestions for further process development. Hence, palm fatty acid distillate (PFAD) has been enzymatically converted to fatty acid methyl esters in a two-step process using the immobilized lipase Novozym 435 in packed-bed columns. With only a small excess of methanol, the first reaction stage could reduce the free fatty acid (FFA) content from 85% to 5%. After removal of water by simple phase separation, it was possible to lower the FFA content to 2.5% in a second reaction stage. Both reaction stages are relatively fast with suggested reaction times of 15 min in column 1 (productivity 10 kg/kg/h) and 30 min in column 2 (productivity 5 kg/kg/h), resulting in 15% FFA after column 1 and 5% FFA after column 2. A lifetime study indicated that approximately 3,500 kg PFAD/kg Novozym 435 can be treated in the first reaction stage before the enzyme has become fully inactivated. With further optimization, the enzymatic process could be a real alternative to today’s sulfuric acid catalyzed process.
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Foidl, N., Foidl, G., Sanchez, M., Mittelbach, M., & Hackel, S. (1996). Jatropha curcas L. as a source for the production of biofuel in Nicaragua. Bioresource Technology, 58, 77–82.
Becker, K., & Makkar, H. (2008). Jatropha curcas: a potential source for tomorrow’s oil and biodiesel. Lipid Technology, 20, 104–107.
Schenk, P. M., Thomas-Hall, S. R., Stephens, E., Marx, U. C., Mussgnug, J. H., Posten, C., et al. (2008). Second generation biofuels: high-efficiency microalgae for biodiesel production. Bioenergy Res, 1, 20–43.
Azam, M. M., Waris, A., & Nahar, N. M. (2005). Prospects and potential of fatty acid methyl esters of some non-traditional seed oils for use as biodiesel in India. Biomass and Bioenergy, 29, 293–302.
Lee, K. T., Foglia, T. A., & Chang, K. S. (2002). Production of alkyl esters as biodiesel fuel from fractionated lard and restaurant grease. Journal of the American Oil Chemists' Society, 79, 191–195.
Van Gerpen, J., & Knothe, G. (2005). Basics of the transesterification reaction. In G. Knothe, J. Krahl, & J. Van Gerpen (Eds.), The biodiesel handbook (pp. 26–41). Champaign: AOCS Press.
Verleyen, T. (2002). Stability of minor components during vegetable oil refining. PhD thesis, Faculty of applied biological sciences. Ghent: Ghent University.
Gibon, V., De Greyt, W., & Kellens, M. (2007). Palm oil refining. European Journal of Lipid Science and Technology, 109, 315–335.
Echim, C., Verhé, R., De Greyt, W., & Stevens, C. (2009). Production of biodiesel from side-stream refining products. Energy & Environmental Science, 2, 1131–1141.
Chongkhong, S., Tongurai, C., Chetpattananondh, P., & Bunyakan, C. (2007). Biodiesel production by esterification of palm fatty acid distillate. Biomass and Bioenergy, 31, 563–568.
Banavali, R. M., Hanlon, R. T., Jerabek, K., & Schultz, A. K. (2009). Heterogeneous catalysis and process for the production of biodiesel from high free-fatty acid-containing feedstocks. In M. Prunier (Ed.), Catalysis of organic reactions (pp. 279–289). New York: CRC Press.
Fjerbaek, L., Christensen, K. V., & Norddahl, B. (2009). A review of the current state of biodiesel production using enzymatic transesterification. Biotechnology and Bioengineering, 102, 1298–1315.
Shimada, Y., Watanabe, Y., Sugihara, A., & Tominaga, Y. (2002). Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing. Journal of Molecular Catalysis. B, Enzymatic, 17, 133–142.
Du, W., Wang, L., & Liu, D. (2007). Improved methanol tolerance during Novozym435-mediated methanolysis of SODD for biodiesel production. Green Chemistry, 9, 173–176.
Holm, H. C., & Cowan, D. (2008). The evolution of enzymatic interesterification in the oils and fats industry. European Journal of Lipid Science and Technology, 110, 679–691.
Rahman Talukder, M. M., Wu, J. C., Lau, S. K., Cui, L. C., Shimin, G., & Lim, A. (2009). Comparison of Novozym 435 and Amberlyst 15 as heterogenous catalyst for production of biodiesel from palm fatty acid distillate. Energy & Fuels, 23, 1–4.
Patkar, S. A., Björking, F., Zundel, M., Schulein, M., Svendsen, A., Heldthansen, H. P., et al. (1993). Purification of 2 lipases from Candida antarctica and their inhibition by various inhibitors. Indian J Chem B, 32, 76–80.
Watanabe, Y., Pinsirodom, P., Nagao, T., Yamaushi, A., Kobayashi, T., Nishida, Y., et al. (2007). Conversion of acid oil by-produced in vegetable oil refining to biodiesel fuel by immobilized Candida antarctica lipase. Journal of Molecular Catalysis. B, Enzymatic, 44, 99–105.
Osório, N. M., da Fonseca, M. M. R., & Ferreira-Dias, S. (2006). Operational stability of Thermomyces lanuginosa lipase during interesterification of fat in continuous packed-bed reactors. Eur J Lipid Sci Tech, 108, 545–553.
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The authors would like to thank Kenny Kestens, thesis student at Karel De Grote Hogeschool (Antwerpen, Belgium) for his work related to this study.
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Brask, J., Damstrup, M.L., Nielsen, P.M. et al. Combining Enzymatic Esterification with Conventional Alkaline Transesterification in an Integrated Biodiesel Process. Appl Biochem Biotechnol 163, 918–927 (2011). https://doi.org/10.1007/s12010-010-9095-9
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DOI: https://doi.org/10.1007/s12010-010-9095-9