Abstract
Glycerolysis of soybean oil was conducted in a supercritical carbon dioxide (SC-CO2) atmosphere to produce monoglycerides (MG) in a stirred autoclave at 150–250°C, over a pressure range of 20.7–62.1 MPa, at glycerol/oil molar ratios between 15–25, and water concentrations of 0–8% (wt% of glycerol). MG, di-, triglyceride, and free fatty acid (FFA) composition of the reaction mixture as a function of time was analyzed by supercritical fluid chromatography. Glycerolysis did not occur at 150°C but proceeded to a limited extent at 200°C within 4 h reaction time; however, it did proceed rapidly at 250°C. At 250°C, MG formation decreased significantly (P<0.05) with pressure and increased with glycerol/oil ratio and water concentration. A maximum MG content of 49.2% was achieved at 250°C, 20.7 MPa, a glycerol/oil ratio of 25 and 4% water after 4 h. These conditions also resulted in the formation of 14% FFA. Conversions of other oils (peanut, corn, canola, and cottonseed) were also attempted. Soybean and cottonseed oil yielded the highest and lowest conversion to MG, respectively. Conducting this industrially important reaction in SC-CO2 atmosphere offered numerous advantages, compared to conventional alkalicatalyzed glycerolysis, including elimination of the alkali catalyst, production of a lighter color and less odor, and ease of separation of the CO2 from the reaction products.
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References
Sonntag, N.O.V., Glycerolysis of Fats and Methyl Esters—Status, Review, and Critique,J. Am. Oil Chem. Soc. 59:795A-802A (1982).
Lauridsen, J.B., Food Emulsifiers: Surface Activity, Edibility, Manufacture, Composition, and Application,53:400–407 (1976).
Swern, D.,Bailey's Industrial Oil and Fat Products, Vol. 2, 4th edn., John Wiley & Sons, New York, 1979, pp. 97–173.
Yamane, T., M.M. Hoq, S. Itoh, and S. Shimizu, Glycerolysis of Fat by Lipase,J. Jpn. Oil Chem. Soc. 35:625–631 (1986).
Stevenson, D.E., R.A. Stanley, and R.H. Furneaux, Glycerolysis of Tallow with Immobilized Lipase,Biotechnol. Lett. 15:1043–1048 (1993).
McNeill, G.P., and R.G. Berger, Enzymatic Glycerolysis of Palm Oil Fractions and a Palm Oil Based Model Mixture,Food Biotech. 7:75–87 (1993).
McNeill, G.P., D. Borowitz, and R.G. Berger, Selective Distribution of Saturated Fatty Acids into the Monoglyceride Fraction During Enzymatic Glycerolysis,J. Am. Oil Chem. Soc. 69:1098–1103 (1992).
McNeill, G.P., and T. Yamane, Further Improvements in the Yield of Monoglycerides During Enzymatic Glycerolysis,68:6–10 (1991).
McNeill, G.P., S. Shimizu, and T. Yamane, High-Yield Enzymatic Glycerolysis of Fats and Oils,68:1–5 (1991).
Yamane, T., M.M. Hoq, S. Itoh, and S. Shimizu, Continuous Glycerolysis of Fat by Lipase in Microporous Hydrophobic Membrane Bioreactor,J. Jpn. Oil Chem. Soc. 35:632–636 (1986).
Van der Padt, A., J.T.F. Keurentjes, J.J.W. Sewalt, E.M. van Dam, L.J. van Dorp, and K. van't Riet, Enzymatic Synthesis of Monoglycerides in a Membrane Bioreactor with an In-line Absorption Column,J. Am. Oil Chem. Soc. 69:748–754 (1992).
Holmberg, K., and E. Osterberg, Enzymatic Preparation of Monoglycerides in Microemulsion,65:1544–1548 (1988).
Nakamura, K., Biochemical Reactions in Supercritical Fluids,Trends in Biotechnol. 8:288–292 (1990).
Aaltonen, O., and M. Rantakylä, Biocatalysis in Supercritical CO2,Chemtech. 21:240–248 (1991).
Perrut, M., Enzymatic Reactions and Cell Behavior in Supercritical Fluids,Chem. Biochem. Eng. Q. 8:25–30 (1994).
Caralp, M.H.M., A.A. Clifford, and S.E. Coleby, inExtraction of Natural Products Using Near-Critical Solvents, edited by M.B. King and T.R. Bott, Blackie Academic & Professional, Glasgow, 1993, pp. 50–83.
Clifford, A.A., inSupercritical Fluids—Fundamentals for Application, edited by E. Kiran and J.M.H. Level Sengers, Kluwer Academic Publishers, Dordrecht, 1994, pp. 449–479.
Kochhar, R.K., and R.K. Bhatnagar, Indian Patent 71,979 (1962).
King, J.W., and G.R. List, A Solution Thermodynamic Study of Soybean Oil/Solvent Systems by Inverse Gas Chromatography,J. Am. Oil Chem. Soc. 67:424–430 (1990).
SAS Institute Inc.,SAS/STAT User's Guide, Version 6, 4th edn., Vol. 2, Cary, 1989.
King, J.W., Fundamentals and Applications of Supercritical Fluid Extraction in Chromatographic Science,J. Chromatogr. Sci. 27:355–364 (1989).
Ashour, I., and H. Hammam, Equilibrium Solubility of Pure Mono-, Di-, and Trilaurin in Supercritical Carbon Dioxide—Experimental Measurements and Model Prediction,J. Supercrit. Fluids 6:3–8 (1993).
Stahl, E., K.W. Quirin, and D. Gerard,Dense Gases for Extraction and Refining, Springer-Verlag, Berlin, 1988, p. 206.
Evelein, K.A., R.G. Moore, and R.A. Heidemann, Correlation of the Phase Behavior in the Systems Hydrogen Sulfide-Water and Carbon Dioxide-Water,Ind. Eng. Chem., Process Des. Dev. 15:423–428 (1976).
Erickson, J.P., P. Schyns, and C.L. Cooney, Effect of Pressure on an Enzymatic Reaction in a Supercritical Fluid,AIChe J. 36:299–301 (1990).
Ross, J., A.C. Bell, C.J. Arrowsmith, and A.I. Gebhart, The Stability and Constitution of Monoglycerides,Oil & Soap 23:257–264 (1946).
McNeill, G.P., S. Shimizu, and T. Yamane, Solid Phase Enzymatic Glycerolysis of Beef Tallow Resulting in a High Yield of Monoglyceride,J. Am. Oil Chem. Soc. 67:779–783 (1990).
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Temelli, F., King, J.W. & List, G.R. Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media. J Am Oil Chem Soc 73, 699–706 (1996). https://doi.org/10.1007/BF02517943
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DOI: https://doi.org/10.1007/BF02517943