Keggin结构磷钼酸及其钠盐催化的二苯并噻吩氧化脱硫反应

 以二苯并噻吩（DBT）为模型化合物和油溶性过氧化氢异丙苯（CHP）作氧化剂，考察了Keggin结构的磷钼酸（H₃PMo₁₂O₄₀）及其钠盐（Na₃PMo₁₂O₄₀）的氧化脱硫性能，并与硅钼酸（H₄SiMo₁₂O₄₀）及磷钨酸（H₃PW₁₂O₄₀）氧化脱硫性能进行对比。结果表明，H₃PMo₁₂O₄₀/SiO₂氧化脱硫活性远高于H₄SiMo₁₂O₄₀/SiO₂，而H₃PMo₁₂O₄₀/SiO₂则基本没有活性。SiO₂担载的磷钼酸及其钠盐催化DBT氧化脱硫反应活性与非负载型催化剂相比有了明显的提高。非负载型磷钼酸及其钠盐以及H₃PMo₁₂O₄₀/SiO₂在催化DBT氧化脱硫反应中都表现出一定的活性诱导期，而Na₃PMo₁₂O₄₀/SiO₂则因其较高的反应活性和CHP有效利用率，并且没有明显诱导期，在DBT氧化脱硫反应中表现出良好的催化性能。

OXIDATIVE DESULFURIZATION OF DIBENZOTHIOPHENE CATALYZED BY Keggin-TYPE H3 PMo12O40 AND Na3PMo12O40

The oxidative desulfurization (ODS) of DBT with cumene hydroperoxode (CHP) as the oxidizing agent over Keggin-type H₃PMo₁₂O₄₀ and Na₃PMo₁₂O₄₀ were studied by comparing with H₄SiMo₁₂O₄₀ and H₃PW₁₂O₄₀. The results indicated that H₃PMo₁₂O₄₀/SiO₂ exhibited much higher ODS activity than H₄SiMo₁₂O₄₀ /SiO₂, whereas H₃PW₁₂O₄₀/SiO₂ showed no activity. The ODS activities of SiO₂ supported H₃PMo₁₂O₄₀ and Na₃PMo₁₂O₄₀ and Na₃PMo₁₂O₄₀ were much higher than their unsupported counter-partners. An induction period was observed during DBT ODS over H₃PMo₁₂O₄0, Na₂PMo₁₂O₄₀ and H₃PMo₁₂O₄₀/SiO₂. Among the catalysts studied in this work, SiO₂ supported Na₃PMo₁₂O₄₀ showed the best catalytic performance due to its high ODS activity, long lifetime, and the absence of the induction period.