二苯并噻吩类硫化物在非负载型NiMoW催化剂上加氢脱硫反应机理

殷长龙; 翟西平; 赵蕾艳; 刘晨光

二苯并噻吩类硫化物在非负载型NiMoW催化剂上加氢脱硫反应机理

中国石油大学(华东)重质油国家重点实验室 CNPC催化重点实验室, 山东青岛 266580

基金项目: 国家重点基础研究发展规划(973计划, 2010CB226905).

详细信息

通讯作者:
殷长龙

中图分类号: O643/TQ53
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出版历程
- 收稿日期: 2013-03-19
- 修回日期: 2013-05-20
- 刊出日期: 2013-08-30

Mechanism of hydrodesulfurization of dibenzothiophenes on unsupported NiMoW catalyst

State Key Laboratory of Heavy Oil Processing, Key Laboratory of Catalysis, CNPC, China University of Petroleum(East China), Qingdao 266580, China

摘要

摘要: 研究了二苯并噻吩(DBT)、4-甲基二苯并噻吩(4-MDBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)在非负载型NiMoW催化剂上的加氢脱硫反应产物分布及反应机理,给出了它们在非负载型催化剂上加氢脱硫反应网络.研究发现,由于甲基的空间位阻效应,二苯并噻吩类化合物加氢脱硫转化率顺序为4,6-DMDBT≈4-MDBT＜DBT,而非负载型NiMoW催化剂具有很高的芳环加氢活性,有利于烷基取代的芳环加氢,减弱空间位阻效应,使烷基取代的二苯并噻吩类化合物得到有效脱除.DBT的脱硫产物会被进一步加氢,其产物分布与联苯加氢产物相似.4-MDBT有两种预加氢脱硫反应路径,甲基取代的苯环由于甲基的供电子效应会被优先加氢.非负载型催化剂存在的L酸中心会使部分4-MDBT和4,6-DMDBT通过脱甲基反应生成DBT再进行脱硫反应.
- 二苯并噻吩 /
- 4-甲基二苯并噻吩 /
- 4,6-二甲基二苯并噻吩 /
- 加氢脱硫 /
- 反应网络 /
- 非负载型NiMoW催化剂
Abstract: Hydrodesulfurization (HDS) of dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) on unsupported NiMoW catalyst was studied. Moreover, mechanisms and reaction networks were revealed on the basis of GC and GC-MS analyses of the reaction products. The result shows that, the HDS rate of dibenzothiophenes is in the order of 4,6-DMDBT≈4-MDBT＜DBT for the spatial restraining effect of the methyl group. Unsupported NiMoW catalyst has high hydrogenation activity in aromatics saturation, it favours the hydrogenation of alkyl-substituted aromatic ring, weakens the spatial restraining effect, leads to the effectively removing of alkyl-substituted dibenzothiophenes. The hydrodesulfurization products of DBT could be hydrogenated further and its distribution is similar to the hydrogenation products of biphenyl(BP). The hydrogenation route of the hydrodesulfurization of 4-MDBT have two reaction pathways, the electron donor induction of the methyl group could promote the hydrogenation of the adjacent phenyl. On the lewis acid sites of catalyst, part of 4-MDBT and 4,6-DMDBT transformed into DBT through the demethylation reaction in their hydrodesulfurization process.
- dibenzothiophene /
- 4-methyldibenzothiophene /
- 4,6-dimethyldibenzothiophene /
- hydrodesulfurization /
- reaction networks /
- unsupported NiMoW catalyst

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参考文献(16)

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