Development and Evaluation of Thermodynamic Models for Predicting Cold Flow Properties of Biodiesel

Biodiesel, especially palm oil-based methyl esters (PME), is steadily increasing in consumption in Indonesia and Malaysia as a petroleum diesel substitute. PME has poor cold flow properties due to the presence of saturated bound glycerols. Bound glycerols, such as monoglycerides (MAGs), diglycerides (DAGs), and triglycerides (TAGs), are impurities in biodiesel as a result of incomplete transesterification, and have high melting points. These minor components often solidify even at temperatures higher than the cloud point and thus cause clogging in fuel filters. It is, therefore, essential to predict the solidification temperature for the application of biodiesel, particularly in high blending levels. This study developed and evaluated thermodynamic models for predicting the solidification of biodiesel. Binary and multicomponent mixtures of fatty acid methyl esters (FAMEs) and bound glycerols were prepared as biodiesel models. The solidification temperature was measured by differential scanning calorimetry and the results were compared with the predicted values. It was discovered that most of the binary mixtures of a FAME and a bound glycerol (MAG, DAG, or TAG) behaved as eutectic systems, in which a solid phase consists of a single component. In the case of the eutectic system, the solidification temperature could be estimated by assuming non-ideal liquid solutions, and the modified UNIFAC (Dortmund) model helped calculate the activity coefficient. However, the mixtures of MAG/MAG differed from the eutectic system, suggesting that the solid compounds of different types of MAGs were formed. Thus, the compound formation model was developed, which was successful in predicting the solidification temperatures of biodiesel model fuels that consist of several kinds of FAMEs and MAGs.