Abstract
Several alcoholysis catalysts, known to be effective for reactions between simple alcohols and soybean oil, were evaluated and found to be ineffective toward alcoholysis of ethylene glycol with soybean oil under traditional reaction conditions. An initial survey of alternative catalysts revealed that organometallic tin complexes were effective but unsatisfactory due to toxicity and difficulty in recovering the catalyst. Satisfactory performance for several alcoholysis reactions was achieved with calcium carbonate catalysts even though at higher temperatures, typically greater than 200°C. Higher reaction temperatures are not considered to be a problem for flow reactors where heat exchangers can be readily used to minimize energy costs. Free fatty acids were esterified by the calcium carbonate and did not appear to inhibit the catalyst. Reaction times of 18 min provided essentially complete conversion. No decrease in the activity of calcium carbonate was observed after weeks of utilization. The robust structure is suitable for use in packed-bed reactors. The catalyst used for the flow reactors was pulverized limestone. Limestone from two locations was tested and found to be effective. Catalyst removal requires only a screening process at the reactor discharge.
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References
Swern, D. (ed.) Bailey’s Industrial Oil and Fat Products Volume 2, Fourth Edition, John Wiley & Sons, New York, 1982, pp. 97–173.
Ma, F., L.D. Clements, and M.A. Hanna, The Effects of Catalyst, Free Fatty Acids, and Water on Transesterification of Beef Tallow, Trans. Am. Soc. Agric. Eng. 41:1261–1264 (1998).
Kawahara, Y., and T. Ono, Process for Producing Lower Alcohol Esters of Fatty Acids, U.S. Patent 4,164,506 (1979).
Stoldt, S.H., and H. Dave, Esters Derived from Vegetable Oils Used as Additives for Fuels, U.S. Patent 5,730,029 (1998).
Siling, M.I., and T.N. Laricheua, Titanium Compounds as Catalysts for Esterification and Transesterification, Russ. Chem. Rev. 65:279–286 (1996).
ascaretti, O.A., and R.L.E. Furlan, Esterifications Transesterifications, and Deesterifications Mediated by Organotin Oxides, Hydroxides, and Alkoxides, Aldrichimica Acta 30:55–68 (1997).
Johnson, R.W., and E. Fritz, Fatty Acids in Industry, Marcel Dekker, Inc., New York, 1989, pp. 139–150.
Stern, R., G. Hillion, J. Rouxel, and S. Leporq, Process for the Production of Esters from Vegetable Oils or Animal Oils Alcohols, U.S. Patent 5,908,946 (1999).
Basu, H.N., and M.E. Norris, Process for Production of Esters for Use as a Diesel Fuel Substitute Using a Nonalkaline Catalyst, U.S. Patent 5,525,126 (1996).
Bettelheim, F.A., and J. Landesberg, Laboratory Experiments for General, Organic & Biochemistry, 3rd edn., Saunders College Publishing, New York, 1998, pp. 353–357.
Suppes, G.J., T.T. Tshung, M.H. Mason, and J.A. Heppert, Performance Advantages of Cetane Improvers Produced from Soybean Oil, Proceedings of the Fourth Biomass Conference of the Americas, DOE Publication, Oakland, CA, 1999, pp. 819–826.
Suppes, G.J., M. Mason, Y.T. Tshung, R. Aggarwal, and J.A. Heppert, Performance Advantages of CI Produced from Soybean Oil, BioEnergy ’98 Conference: Expanding, Bioenergy Partnerships, Madison, WI, Biomass Publications, Chicago, 1998, pp. 1022–1031.
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Suppes, G.J., Bockwinkel, K., Lucas, S. et al. Calcium carbonate catalyzed alcoholysis of fats and oils. J Amer Oil Chem Soc 78, 139–146 (2001). https://doi.org/10.1007/s11746-001-0234-y
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DOI: https://doi.org/10.1007/s11746-001-0234-y