Transformation of non-edible vegetable oils into biodiesel fuels catalyzed by unconventional sulfonic acid-functionalized SBA-15

Abstract

A real understanding of intrinsic acidity and catalytic property of unconventional and sulfonic acid-functionalized SBA-15 platelet catalysts synthesized with the aid of highly solvated Zr4+ salts (shortly termed SA-SBA-15-p) for transesterification of non-edible vegetable oils into biodiesel fuel (BDF) was reported, in comparison with conventional SBA-15 catalyst (shortly termed SBA-15-conv), unconventional SBA-15 platelet catalyst (shortly termed SBA-15-p) and commercial sulfonic resins of Amberlyst-15 and SAC-13. Thorough characterizations and catalytic study revealed that the content of fatty acid methyl ester (FAME) as the main component of BDF was increased in the order of SBA-15-conv<SAC-13<SBA-15-p<Amberlyst-15<5-25SA-SBA-15-p, which correlated closely with the loading, distribution, strength of acidic sites. Among them, the unconventional 15SA-SBA-15-p catalyst with proper loadings of propylsulfonic groups (1.15mmolS−1g−1) and superficial Zr4+ clusters (0.66mmolg−1) as a mixed solid Bronsted and Lewis acid, which had differential heat of NH3 adsorption in the range of 90–125kJmol−1, gave highest FAME content with low concentrations of byproducts, such as glycerides and free fatty acid (FFA). In addition to high water and FFA tolerance levels, the used 15SA-SBA-15-p catalyst could be easily regenerated by ethanol extraction and its high activity was maintain. By contrast, the SBA-15-conv catalyst without any Lewis and Bronsted acids had almost no activity in BDF synthesis. The unconventional SBA-15-p catalyst with superficial Zr4+ clusters as a pure solid Lewis acid gave a moderate FAME content accompanying with a high concentration of unreactive glycerides. Commercial sulfonic resins of Amberlyst-15 and SAC-13 with strongly phenylsulfonic and Nafion sulfonic groups as pure solid Bronsted acids gave moderate FAME contents accompanying with high concentrations of unreactive glycerides and unwanted FFA byproducts. Furthermore, they were significantly deactivated by water, FFA and regeneration treatment due to the poison and leaching of sulfonic groups and the decomposition of thermally unstable framework.