Department of Petroleum Chemistry and Organic Catalysis, Moscow State University, 119991 Moscow, Russia.
Department of Physical and Colloid Chemistry, Gubkin Russian State University of Oil and Gas, 119991 Moscow, Russia.
Molecules. 2020 Jan 26;25(3):536. doi: 10.3390/molecules25030536.
Polyoxometalate-based ionic liquid hybrid materials with a pyridinium cation, containing Brönsted acid sites, were synthesized and used as catalysts for the oxidation of model and real diesel fuels. Keggin-type polyoxometalates with the formulae [PMoO], [PVMoO], [PVMoO], [PWO] were used as anions. It was shown that increasing the acid site strength leads to an increase of dibenzothiophene conversion to the corresponding sulfone. The best results were obtained in the presence of a catalyst, containing a nicotinic acid derivative as cation and phosphomolybdate as anion. The main factors affecting the process consisting of catalyst dosage, temperature, reaction time, oxidant dosage were investigated in detail. Under optimal conditions full oxidation of dibenzothiophene and more than a 90% desulfurization degree of real diesel fuel (initial sulfur content of 2050 ppm) were obtained (the oxidation conditions: NK-1 catalyst, molar ratio HO:S 10:1, molar ratio S:Mo 8:1, 1 mL MeCN, 70 °C, 1 h). The synthesized catalysts could be used five times with a slight decrease in activity.
基于聚阴离子的离子液体杂化材料，其阳离子为吡啶，含有 Brönsted 酸位，被合成并用作模型和实际柴油燃料氧化的催化剂。采用 Keggin 型多金属氧酸盐作为阴离子，其化学式为[PMoO]、[PVMoO]、[PVMoO]和[PWO]。结果表明，增加酸位强度会导致二苯并噻吩向相应砜的转化率增加。在含有烟碱酸衍生物作为阳离子和磷钼酸盐作为阴离子的催化剂存在下，获得了最佳的结果。详细研究了影响该过程的主要因素，包括催化剂用量、温度、反应时间和氧化剂用量。在最佳条件下，可获得二苯并噻吩的完全氧化和实际柴油燃料（初始硫含量为 2050 ppm）的脱硫率超过 90%（氧化条件：NK-1 催化剂，HO:S 摩尔比为 10:1，S:Mo 摩尔比为 8:1，1 mL MeCN，70°C，1 h）。合成的催化剂可以重复使用五次，活性略有下降。
