Hexacyanoferrate‐based ionic liquids as Fenton‐like catalysts for deep oxidative desulfurization of fuels

Abstract

Two hexacyanoferrate‐based ionic liquids, [C4Py]3Fe(CN)6 and [C16Py]3Fe(CN)6, were synthesized and characterized using Fourier transform infrared and mass spectroscopies and CHN analysis. They were employed as Fenton‐like catalysts in extraction and catalytic oxidative desulfurization of model oil with dibenzothiophene (DBT), benzothiophene (BT), 4,6‐dimethyldibenzothiophene (4,6‐DMDBT), 4‐methyldibenzothiophene (4‐MDBT) and 3‐methylbenzothiophene (3‐MBT) as substrates. Various polar solvents, such as ionic liquids, water and organic solvents, were applied to choose a suitable extractant. The results showed the removal of DBT reached 97.1% with [C4Py]3Fe(CN)6 as a catalyst and 1‐n‐octyl‐3‐methylimidazolium hexafluorophosphate ([C8mim]PF6) as an extractant under optimal conditions. The activity of sulfur removal followed the order DBT > 3‐MBT > BT > 4‐MDBT >4,6‐DMDBT. The effect of water content on sulfur removal was investigated by adding various concentrations of H2O2. It was found that excess water had a positive effect on sulfur removal but the catalysts were less sensitive than [FeCl4−]‐based catalysts to water. The mechanism was studied using electron spin‐resonance spectroscopy and gas chromatography–mass spectrometry. O2•− may be the active oxygen species in the catalytic oxidative desulfurization process and the oxidation products of various sulfur compounds were the corresponding sulfoxides and sulfones. Copyright © 2016 John Wiley & Sons, Ltd.