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论文类型：期刊论文

发表时间：2011-04-01

发表刊物：TOPICS IN CATALYSIS

收录刊物：SCIE、EI

卷号：54

期号：5-7

页面范围：290-298

ISSN号：1022-5528

关键字：Hydrodesulfurization; Dibenzothiophene; Hydrogenated intermediates; Nickel phosphide; Piperidine; Mechanism

摘要：A bulk Ni2P catalyst was prepared by co-precipitation of nickel phosphate followed by in situ temperature-programmed reduction (TPR) with H-2. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) and its hydrogenated intermediates 1,2,3,4-tetrahydro-dibenzothiophene (TH-DBT) and 1,2,3,4,4a, 9b-hexahydro-dibenzothiophene (HH-DBT) was studied at 340 degrees C and 4 MPa both in the presence and absence of piperidine (Pi). Bulk Ni2P exhibited a relatively low hydrogenation/dehydrogenation activity but high desulfurization activity. Pi retarded the hydrogenation of DBT to a greater extent than the desulfurization. The desulfurization of HH-DBT to 2-cyclohexen-1-yl-benzene (CHEB-2) occurred mainly by beta-elimination of the hydrogen atom attached to carbon atom C(4), whereas TH-DBT desulfurized mainly by hydrogenolysis to 1-cyclohexen-1-yl-benzene (CHEB-1). A minor amount of biphenyl (BP) observed in the HDS of TH-DBT and HH-DBT is due to the disproportionation of cyclohexenyl-benzenes. A reaction network of the HDS of DBT over Ni2P is postulated in which both beta-elimination and hydrogenolysis play a role in the breaking of the C-S bonds.