Designing multifunctional SO3H-based polyoxometalate catalysts for oxidative desulfurization in acid deep eutectic solvents
Designing multifunctional SO3H-based polyoxometalate catalysts for oxidative desulfurization in acid deep eutectic solvents
复制标题
设计用于酸性低共熔溶剂中氧化脱硫的多功能 SO3H 基多金属氧酸盐催化剂
DOI：
10.1039/c7ra10125b
复制
发表时间：
2017-01-01
期刊：
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;Dong, Lei;Li, Huaming
深共晶溶剂（DESs）是具有广泛应用的“绿色”可持续溶剂，如燃料的萃取脱硫；但其萃取效率低是制约其应用的主要因素。本文制备了几种so3h功能化的多金属氧酸盐，并将其应用于以酸性DESs为萃取剂，30% H2O2为氧化剂的燃料氧化脱硫。与中性POM催化剂相比，[PSTEtA]3PW(12)O（40）等酸性催化剂表现出更高的催化性能，脱硫效率为100%。然而，在没有DESs的情况下，使用[PSTEtA](3)PW12O40作为催化剂，硫的去除率仅为9.6%。为了研究DESs对二苯并噻吩（DBT）的萃取和氧化作用，考察了三种DESs对DBT的萃取和氧化作用，其中酸性DES ChCl/2Ac的萃取和氧化性能最好。考察了H2O2用量、ChCl/2Ac用量、反应温度、反应时间、硫化物种类、燃料组成等不同反应条件的影响。结合动力学研究结果表明，DBT的氧化反应属于准一级动力学反应。不同含硫化合物的活性依次为DBT > 3-甲基苯并噻吩(3-MBT) > 4-甲基二苯并噻吩(4- mdbt) > 4,6-二甲基二苯并噻吩(4,6- dmdbt) >苯并噻吩（BT）。与芳烃相比，烯烃对硫的去除率影响较大，可达66.6%。
Deep eutectic solvents (DESs) are 'green' sustainable solvents with wide applications such as extractive desulfurization of fuel; however, their low extraction efficiency is a major limitation to such applications. In this work, several SO3H-functionalized polyoxometalates were prepared and applied to oxidative desulfurization of fuels with acidic DESs as extractants and 30 wt% of H2O2 as an oxidant. Compared with neutral POM catalysts, acidic catalysts, such as [PSTEtA]3PW(12)O(40), exhibited higher catalytic performance with 100% desulfurization efficiency. However, in the absence of DESs sulfur removal was only 9.6% with [PSTEtA](3)PW12O40 used as a catalyst. To study the role of the DESs, three types of DESs were evaluated on extraction and oxidation of dibenzothiophene (DBT), with acidic DES ChCl/2Ac exhibiting the best performance. The effects of different reaction conditions, such as the amount of H2O2 and ChCl/2Ac, reaction temperature and time, different sulfur compounds, and fuel composition, were investigated. Combined with the kinetic study, results suggested that oxidation of DBT was attributed to a pseudo-first-order kinetic reaction. The activities of different sulfur compounds decreased in the order of DBT > 3-methylbenzothiophene (3-MBT) > 4-methyldibenzothiophene (4-MDBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). Compared with aromatics, the sulfur removal could be strongly affected by olefins, showing a drop of up to 66.6%.