中文摘要：

合成了四种有机一无机型杂多酸催化剂，包括[Ⅱ-C5H5NC16H33]3[PW4O16]，[π-C5HsNCl6H33]3[PMo4O16]，[π-CsHsNCl2H25]3[PW4O16]和[π—C5H5NCl2H25]3[PM04016]．以有机硫的正辛烷溶液为模拟油品，H202为氧化剂，乙腈为萃取剂，在两相体系中，考察了上述四种催化剂对模拟油品中二苯并噻吩（DBT）氧化脱硫的催化活性．结果表明，[Ⅱ-CsHsNCl6H33]3[PW4O16]具有最佳的催化活性．采用[π-C5HsNCl6H33]3[PW4O16]进行后续研究发现，反应完毕，[π-CsH5NCl6H33]3[PW4O16]以沉淀的形式析出，可以重复利用且脱硫效果很好．研究表明，上述有机一无机型杂多酸属于相转移催化剂，氧化脱硫反应体系属于反应控制相转移催化体系．在相同实验条件下，由于电子云密度和空间位阻效应共同的作用，DBT、噻吩（TH）、苯并噻吩（BT）和4，6-二甲基二苯并噻吩（4，6-DMDBT）脱硫由易到难的顺序为DBT〉4,6．DMDBT〉BT〉TH，并分别通过GC—MS分析确定它们的氧化产物．将[π-C5H5NCl6H33]3[PW4016]进一步应用于柴油氧化脱硫，其中硫含量由355mg／kg（mg／kg等同于ppmw）降至26mg／kg，去除率达92．7％．利用上述四种有机一无机型杂多酸作催化剂，研究DBT氧化反应过程动力学，确定DBT的表观反应级数均为一级，表观活化能为47．9～55．4kJ／mol．

英文摘要：

In this paper, organic-inorganic heteropolyacids were prepared, including [π-CsH5NC16H3313[PW4O16], [π-CsHsNC16H3313[PM04O16], [rr-CsHsNC12H2513[PW4O16] and [π-CsHsNC12H2513[PM04O16]. The efficiency of oxidative desulfurization was investigated on the four kinds of catalysts under the same conditions using the simulated oil prepared by dissolving organo-sulfur in normal octane. The results show that the catalytic activity of [π-CsHsNC16 H3313[PW4016] is the best. The catalytic activity of these heteropolyacids was following the order of [π-C5HsNC16H3313[PW4016] ~ [n-CsHsNC12H2513[PW4016]〉[~-CsHsNCI6H3313[PMo4OI6]〉[π-CsHsNC12H2513[PM04OI6]. Under the optimal experimental conditions, pre-reaction time between H202 and the catalyst being 10 min, reaction temperature being 60 C, O/S molar ratio being 10, the amount of catalyst being 1 wt% of n-octane, and the catalyst being [n-CsHsNC16H3313[PW4O16], the diben- zothiophene （DBT） conversion was nearly 100% after 60 rain. The catalyst [π-C5HsNCI6H3313[PW4016] can be reclaimed by auto precipitation due to the exhausting of 1-1202. The results show that organic-inorganic heteropolyacids are phase transfer catalyst and oxidative desulfurization system belongs to the phase transfer catalysis system controlled by reaction. The cata- lytic activity of the recycled [π-CsHsNC16H3313[PW4016] is almost the same as the fresh. Then, the efficiency of oxidative desulfurization was investigated with different simulated oils using DBT, thiophene （TH）, benzothiophene （BT） and 4,6-dimethyldibenzothiophene （4,6-DMDBT）, respectively. Under the same conditions, the efficieneies of oxidative desulfu- rization decrease in the order of DBT〉4,6-DMDBT〉BT〉TH, the result was influenced by electron density on the sulfur atoms and the sterie hindrance. It showed that the final desulfurization product of TH, BT, DBT and 4,6-DMDBT was SO]-, SO42-, DBT sulphone and 4,6-DMDBT sulphone, respectively. [π-CsH5NC16H3313[PW4016] used in desulfurization of the real diesel a