This study reports on a novel two-step process for biodiesel production consisting of hydrolysis of oils in sub-critical water and subsequent supercritical dimethyl carbonate esterification. This process found to occur optimally at the sub-critical water treatment (270 degrees Celsius/27 MPa) for 25 min followed by a subsequent supercritical dimethyl carbonate treatment (300 degrees Celsius/9 MPa) for 15 min to achieve a comparably high yield of fatty acid methyl esters, at more than 97 wt%. In addition, the fatty acid methyl esters being produced satisfied the international standard specifications for use as biodiesel fuel. This new process for biodiesel production offers milder reaction condition (lower temperature and lower pressure), non-acidic, non-catalytic and applicable to feedstock with high amount of free fatty acids such as crude Jatropha curcas oil.
In this study, the non-catalytic supercritical method has been studied in utilizing dimethyl carbonate. It was demonstrated that, the supercritical dimethyl carbonate process without any catalysts applied, converted triglycerides to fatty acid methyl esters with glycerol carbonate and citramalic acid as by-products, while free fatty acids were converted to fatty acid methyl esters with glyoxal. After 12 min of reaction at 350 °C/20 MPa, rapeseed oil treated with supercritical dimethyl carbonate reached 94% (w/w) yield of fatty acid methyl ester. The by-products from this process which are glycerol carbonate and citramalic acid are much higher in value than glycerol produced by the conventional process. In addition, the yield of the fatty acid methyl esters as biodiesel was almost at par with supercritical methanol method. Therefore, supercritical dimethyl carbonate process can be a good candidate as an alternative biodiesel production process.
The production of glycerol as a by-product is unavoidable in the current conventional biodiesel manufacturing processes. Since biodiesel production is expected to increase in the near future, effective utilization of glycerol will become an issue of interest. In this study, therefore, a process consisting of subcritical acetic acid treatment to convert rapeseed oil to fatty acids and triacetin followed by conversion of the obtained fatty acids to their fatty acid methyl esters in supercritical methanol treatment was investigated. The obtained results clearly revealed that this two-step reaction could proceed effectively at a high reaction rate, and that fatty acid methyl esters and triacetin could be obtained under milder reaction condition than the one-step process utilizing supercritical methyl acetate and supercritical methanol.
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