MCM-41分子筛负载亚硒核过氧钨酸盐催化剂催化二苯并噻吩氧化脱硫

doi:10.1016/S1872-2067(15)60897-X

摘要/Abstract

摘要：

石油在作为燃料使用过程中常常产生各种污染, 特别是油品中的含硫化合物不仅会降低油品品质, 而且燃烧后产生的硫氧化物可污染大气, 形成酸雨, 危害人类健康. 因此, 油品深度脱硫是一项十分重要而紧迫的工作.
目前油品脱硫方法有很多种, 主要分为加氢脱硫与非加氢脱硫. 加氢脱硫反应条件苛刻, 脱硫效率低, 对设备要求高, 因而非加氢脱硫正在被广泛研究. 其中氧化脱硫反应条件温和, 脱硫效率高, 对设备要求不高, 有望实现规模化应用. 在氧化脱硫反应中, 催化剂是研究重点, 尤其是催化剂效率及可回收能力. 本课题组合成的亚硒核过氧钨酸盐是一种具有高选择性和高催化活性的催化剂, 但它在反应后无法实现回收再利用, 从而限制了其广泛应用. 为了提高该催化剂的可回收能力, 本文尝试制备负载型亚硒核过氧钨酸盐用于氧化脱硫反应中, 考察其催化效率及可回收能力.
分子筛具有孔结构, 比表面积大且较为稳定, 是理想的催化剂载体. 本文采用浸渍法制备了MCM-41分子筛负载的亚硒核过氧钨酸盐, 为了提高负载能力, 减少催化剂溶脱, 还制备了MCM-41-NH₂分子筛负载的亚硒核过氧钨酸盐, 并运用红外光谱、X射线衍射、N₂吸附-脱附和透射电镜对它们进行了表征. 结果显示, 亚硒核过氧钨酸盐在MCM-41和MCM-41-NH₂分子筛内分散均匀, 表明负载成功. 将负载型亚硒核过氧钨酸盐催化剂用于模拟油样二苯并噻吩(DBT)氧化脱硫实验, 并用气相-火焰光度检测仪跟踪实验. 结果表明, 负载型和非负载型催化剂均具有较高的催化性能. 模拟油样在负载型催化剂作用下氧化脱硫反应2 h后, DBT转化率达98.7%, 实现了深度脱硫. 此外, 还优化了反应时间、反应温度及氧化剂和催化剂用量. 与其它催化剂相比, 在相似脱硫效率情况下, 负载型催化剂的催化效率更高, 反应条件更加温和, 催化剂用量更少, 因而更加环保和节能. 对反应产物进行了红外光谱、气相-质谱联用分析以及气相色谱保留时间对比分析, 结果表明DBT脱硫反应产物为DBTO₂. 结合相关文献, 对该催化剂上DBT氧化脱硫提出了一种可能的催化氧化反应机理.
反应后将负载型催化剂回收过滤, 洗涤和干燥后, 进行下一轮氧化脱硫反应. 结果表明, MCM-41分子筛负载的亚硒核过氧钨酸盐在循环使用过程中, DBT转化率下降较快, 循环使用4次后, DBT转化率降至80%, 而MCM-41-NH₂分子筛负载的催化剂在循环使用4次后, DBT转化率仍达90%. 这表明MCM-41-NH₂分子筛负载的亚硒核过氧钨酸盐催化剂具有更好的稳定性和回收使用性能.
综上所述, 负载型亚硒核过氧钨酸盐是一种高效的氧化脱硫催化剂, 在较为温和的反应条件下即可实现深度催化氧化脱硫, 其循环使用性能也得到明显提高. 本结果可为该催化剂未来在工业上广泛应用提供一定参考.

关键词: 二苯并噻吩, 氧化脱硫, 亚硒核过氧钨酸盐, MCM-41分子筛

Abstract:

Catalysts play an important role in oxidative desulfurization, a promising process for producing cleaner fossil fuels for transport. A highly efficient catalyst, Q₄-H₂Se^IV₃W₆, for the oxidative desulfurization of dibenzothiophene (DBT) was reported in 2011. To comprehensively evaluate this catalyst and better understand its recovery, two types of the catalyst were prepared by impregnating Q₄-H₂Se^IV₃W₆on MCM-41 and functionalized MCM-41 materials. In the oxidative desulfurization process catalyzed by these supported catalysts, the conversion of DBT reached 98.7%. The catalytic activities were excellent when Q₄-H₂Se^IV₃W₆ was impregnated on functionalized MCM-41. The results showed that the supported catalysts had excellent reusability. In addition, a mechanism for the catalytic oxidative desulfurization was proposed.

Key words: Dibenzothiophene, Oxidative desulfurization, Peroxotungstate, MCM-41

谢东, 何其慧, 苏阳洋, 王童薇, 许仁富, 胡柏星. MCM-41分子筛负载亚硒核过氧钨酸盐催化剂催化二苯并噻吩氧化脱硫[J]. 催化学报, 2015, 36(8): 1205-1213.

Dong Xie, Qihui He, Yangyang Su, Tongwei Wang, Renfu Xu, Baixing Hu. Oxidative desulfurization of dibenzothiophene catalyzed by peroxotungstate on functionalized MCM-41 materials using hydrogen peroxide as oxidant[J]. Chinese Journal of Catalysis, 2015, 36(8): 1205-1213.

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https://www.cjcatal.com/CN/Y2015/V36/I8/1205

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