Hexacyanoferrate-based ionic liquids as Fenton-like catalysts for deep oxidative desulfurization of fuels
Hexacyanoferrate-based ionic liquids as Fenton-like catalysts for deep oxidative desulfurization of fuels
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六氰基铁酸盐基离子液体作为类芬顿催化剂用于燃料深度氧化脱硫
DOI：
10.1002/aoc.3500
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发表时间：
2016
影响因子：
3.9
通讯作者：
Li Huaming
中科院分区：
文献类型：
--
作者：
Jiang Wei;Li Hongping;Yin Sheng;Wang Xin;Liu Wei;Liu Hui;Zhu Wenshuai;Li Huaming
合成了两种铁氰化物基离子液体[C4 Py]3Fe（CN）6和[C16 Py]3Fe（CN）6，并通过傅立叶变换红外光谱、质谱和CHN分析对其进行了表征。以二苯并噻吩（DBT）、苯并噻吩（BT）、4，6-二甲基二苯并噻吩（4，6-DMDBT）、4-甲基二苯并噻吩（4-MDBT）和3-甲基苯并噻吩（3-MBT）为底物，将其作为类芬顿催化剂，对模拟油进行萃取和催化氧化脱硫研究。采用离子液体、水、有机溶剂等极性溶剂对萃取剂进行了筛选。结果表明，以[C4 Py]3Fe（CN）6为催化剂，1-正辛基-3-甲基咪唑六氟磷酸盐（[C8 mim] PF 6）为萃取剂，在最佳条件下，DBT的去除率可达97.1%。脱硫活性大小顺序为DBT > 3-MBT > BT > 4-MDBT > 4，6-DMDBT。通过加入不同浓度的H2 O2，考察了水含量对脱硫效果的影响。结果发现，过量的水对脱硫有积极影响，但催化剂对水的敏感性低于[FeCl 4 −]基催化剂。使用电子自旋共振光谱和气相色谱-质谱法研究了其机理。O2·−可能是催化氧化脱硫过程中的活性氧物种，各种硫化物的氧化产物为相应的亚砜和砜。版权所有© 2016约翰威利父子有限公司.
Two hexacyanoferrate‐based ionic liquids, [C4Py]3Fe(CN)6and [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)6as 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.