Use of supercritical methanol/carbon dioxide mixtures for biodiesel production

The use of supercritical conditions for the production of biodiesel from both vegetables oils and waste-oils may be of great industrial interest because it can be carried out without those catalysts necessary in the conventional transesterification process, therefore avoiding a complex separation between the product and the catalyst. However, the use of supercritical alcohol requires higher operating temperatures and pressures. In this work, CO2 was added to the reaction mixture in order to reduce the operating conditions (temperature, pressure and molar ratio of alcohol to vegetable oil). The novelty of using CO2 may have two advantages: a possible combination of supercritical CO2 extraction of the oil and its subsequent transesterification reaction without CO2 depressurization, and a reduction of the supercritical temperature and pressure of the mixture. The effects of temperature (280-350 A degrees C), pressure (140-280 bar), methanol-to-oil molar ratio (20-30), CO2-to-methanol molar ratio (0.05-0.2) and residence time (0-45minutes) on the yield of methyl esters (biodiesel) were studied in a batch reactor, obtaining in all cases a relatively low increase in the yield when CO2 was present in the medium. The yields of biodiesel were tested with three vegetable oils used as model compounds (palm, sunflower and borage), obtaining similar results.