Citation: YIN Chang-long, ZHAI Xi-ping, ZHAO Lei-yan, LIU Chen-guang. Mechanism of hydrodesulfurization of dibenzothiophenes on unsupported NiMoW catalyst[J]. Journal of Fuel Chemistry and Technology, ;2013, 41(8): 991-997. shu

Mechanism of hydrodesulfurization of dibenzothiophenes on unsupported NiMoW catalyst

1.
State Key Laboratory of Heavy Oil Processing, Key Laboratory of Catalysis, CNPC, China University of Petroleum(East China), Qingdao 266580, China

Corresponding author: YIN Chang-long,
Received Date: 19 March 2013
Available Online: 20 May 2013
Fund Project: 国家重点基础研究发展规划(973计划, 2010CB226905). (973计划, 2010CB226905)

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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沈阳化工大学材料科学与工程学院沈阳 110142