Towards continuous sustainable processes for enzymatic synthesis of biodiesel in hydrophobic ionic liquids/supercritical carbon dioxide biphasic systems

The excellent suitability of immobilized Candida antarctica lipase B (Novozym 435) catalyst to carry out the synthesis of methyl oleate (biodiesel) by methanolysis of triolein in ILs based on imidazolium cations with large alkyl side chain (from C-12 to C-18) has been demonstrated at 60 and 85 degrees C. The phase behaviour of IL/triolein/methanol and IL/methyl oleate mixtures were studied at different concentrations and temperatures, the best results (up to 98.6% biodiesel yield after 6 h) being obtained for ILs able to provide monophasic reaction systems, i.e. 1-methyl-3-octadecylimidazolium bis(trifluoromethylsulfonyl)imide). A continuous enzymatic reactor, based on biocatalysts particles coated with hydrophobic ILs, for biodiesel synthesis in supercritical carbon dioxide was studied at 60 degrees C and 180 bar. The operational stability of the immobilized lipase was improved by its coating with ILs, i.e. 1-methyl-3-octadecylimidazolium hexafluorophosphate, leading to a two-phase systems with respect to the biodiesel product, which showed an excellent catalytic behaviour in continuous operation under supercritical conditions (up to 82% biodiesel yield after 12 cycles of 4 h). (C) 2011 Elsevier Ltd. All rights reserved.