Partial hydrothermal oxidation of unsaturated high molecular weight carboxylic acids for enhancing the cold flow properties of biodiesel fuel

Biodiesel fuel has become more attractive recently because of its environmental benefits and the fact that it is a product made from renewable resources. However the less favorable cold flow properties or the low temperature operability of biodiesel fuel compared to conventional diesel is a major drawback limiting its use. The poor flow properties of biodiesel at cold temperatures are mainly due to biodiesel fuel being composed of long-chain fatty acids with an alcohol molecule attached. If the double bond of unsaturated fatty acids in these long-chain fatty acids could be ruptured selectively, then the cold flow properties of biodiesel fuel would be enhanced by reducing its viscosity.In this study, the selective hydrothermal oxidation of oleic acid, as a model compound of unsaturated high molecular weight carboxylic acids, was studied experimentally. The objective was to use this as a model to investigate whether the double bond of unsaturated fatty acids can be ruptured selectively by partial hydrothermal oxidation. Demonstration of this method could then be used to show the potential to improve the cold flow properties of biodiesel. Results showed that the amount of mono-carboxylic acids, aldehyde, di-carboxylic acids, and aldehyde-acids with a carbon number of 9 was significantly higher than other oxidative products. This suggests that the oxidative cleavage may principally occur at the double bond in hydrothermal conditions. The cloud and pour points for biodiesel fuel (B100) and B100 blend with a mixture of methyl esters or acetals were measured. These are the most important indicators for the cold flow properties of biodiesel fuel. The methyl esters or acetals used were made from the esterification of carboxylic acids or aldehydes by simulating the major oxidation products. These were obtained from the hydrothermal oxidation of oleic acid at different oxygen supply rates. Results showed that the cloud and pour points of the blend were significantly enhanced compared to those of B100.