Phase distributions of alcohol, glycerol, and catalyst in the transesterification of soybean oil

Two‐phase base‐catalyzed transesterification of vegetable oils is the most common method for making biodiesel. The reaction starts as separate oil and alcohol phases. At the end of the reaction, the mixture, if allowed to settle, consists of an upper ester‐rich layer and a lower glycerol‐rich layer. The compositions of these layers from the methanolysis and ethanolysis of soybean oil were measured. Synthetic mixtures and actual reaction mixtures were used either to represent or generate steadystate reaction mixtures resulting from the initial condition of 6∶1 alcohol/oil molar ratio and catalyst concentration (1.0 wt% sodium methoxide or 1.26 wt% sodium ethoxide). At 23°C, for methanolysis, 42.0% of the alcohol, 2.3% of the glycerol, and 5.9% of the catalyst were in the ester‐rich phase at steady state. In ethanolysis, 75.4% of the ethanol, 19.3% of the glycerol, and 7.5% of the catalyst were in the ester‐rich phase. The volume of the glycerol‐rich phase decreased from methanolysis to ethanolysis to propanolysis; butanolysis remained monophasic throughout. The results explain some of the general kinetic behavior observed in transesterifications and provide useful information for alcohol recovery and product purification.