Phase behavior of the base-catalyzed transesterification of soybean oil

Biodiesel is made by the transesterification of vegetable oils to form alkyl FA esters. High levels of conversion (>99%) are required to lower the total concentration of free and chemically bound glycerol to that allowed by the ASTM standard (0.240 wt%) for biodiesel. A polar dye was used to visualize the phase behaviors in methanolysis, ethanolysis, and butanolysis. The dye was more strongly colored in more polar phases. Methanolysis and ethanolysis reactions commenced as two phases (alcohol and oil), then formed emulsions, and ended as two phases as glycerol-rich phases separated. Ethanolysis was more easily initiated by mixing than was methanolysis. Ethanolysis also exhibited a much longer emulsion period and slower glycerol separation. The glycerol-rich phase was smaller in volume in ethanolysis than in methanolysis. Butanolysis remained one phase throughout, and no polar phase existed at any time. The results are consistent with the known phase compositions in these reactions. The concentrations of MG, DG, and TG in the products with time in stirred reactions were consistent with the observed phase behavior in the dye experiments.