Hydrodesulfurization catalyzed by zeolite-supported

沸石负载催化加氢脱硫

• 批准号: 08455370
• 负责人: TATSUMI Takashi
• 金额: $ 1.73万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455370/
• 关键词: Hydrodesulfurization; Molybdenum catalyst; Nikkel catalyst; Zeolite; Ion exchange; Cluster; Methyl transfer; Demethylation; モリブデン触媒

We intended to promote the hydrodesulfurization reactivity of dimethyldibenzothiophenes, 4,6-dimethyldibenzothiophene, in particular, by utilizing the acidity of zeolites, which promotes demethylation or methyl-transfer reaction. We have successfully incorporated a molybdenum sulfide cluster, [Mo_3S_4(H_2O)_9]^<4+> with incomplete cubane-type structure and molybdenum-nickel cluster with complete cubane-type structure into zeolites with 12-membered ring by aqueous ion exchange. Control catalysts Mo/Al_2O_3 and MoNi/Al_2O_3 were also prepared by impregnating Al_2O_3 with the solution of ammonium heptamolybdate and nickel nitrate followed by presulfiding. In the preparation of Mo/KL and Mo-MOR,the ion exchange was found to be sluggish and the degree of exchange was as low as 20%. However, Mo/KL and showed higher HDS activity than Mo/NaY in spite of its lower molybdenum loading. Involvement of Ni resulted in great enhancement of HDS activity ; however, MoNi/KL proved to be less active for HDS of benzothiophene than NiS-MoS_2/Al_2O_3 catalyst. In contrast, MoNi/KL showed higher activity for HDS of 4,6-dimethylbenzothiophene than NiS-MoS_2/Al_2O_3 catalyst. From the analysis of the product distribution, it is concluded that this high activity of MoNi/KL is due to the conversion of the reactant to more reactive ones through demethylation or methyl-transfer reaction promoted by acidity of the catalyst.

我们旨在提高二甲基二苯并噻吩、4,6-二甲基二苯并噻吩的加氢脱硫反应活性，特别是利用沸石的酸性，促进脱甲基或甲基转移反应。我们通过水离子交换的方法，成功地将不完全立方烷型结构的硫化钼团簇[Mo_3S_4(H_2O)_9]^<4+>和完全立方烷型结构的钼镍团簇掺入十二元环沸石中。将七钼酸铵和硝酸镍溶液浸渍Al_2O_3并预硫化制备了对照催化剂Mo/Al_2O_3和MoNi/Al_2O_3。在Mo/KL和Mo-MOR的制备中，发现离子交换缓慢，交换度低至20%。然而，尽管 Mo/KL 的钼负载量较低，但 Mo/KL 却表现出比 Mo/NaY 更高的 HDS 活性。 Ni的参与使得HDS活性大大增强；然而，MoNi/KL对苯并噻吩的HDS活性低于NiS-MoS_2/Al_2O_3催化剂。相比之下，MoNi/KL对4,6-二甲基苯并噻吩的HDS表现出比NiS-MoS_2/Al_2O_3催化剂更高的活性。从产物分布的分析可以得出结论，MoNi/KL 的高活性是由于催化剂的酸性促进的去甲基化或甲基转移反应将反应物转化为更具活性的反应物。

项目成果

T.Tatsumi, M.Taniguchi, S.Yasuda, Y.Ishii, T.murata, M.Hidai: "Zeolite-supported hydrodesulfurzation catalysts prepared by ion exchangewith MO and Np-Ni sulfide clusters" Applied Catalysis. 139. L5-L10 (1996)

T.Tatsumi、M.Taniguchi、S.Yasuda、Y.Ishii、T.murata、M.Hidai：“通过与 MO 和 Np-Ni 硫化物簇进行离子交换制备的沸石负载加氢脱硫催化剂”应用催化。

M.Taniguchi, S.Yasuda, Y.Isii, I.Murata, M.Hidai, T.Tatsumi: "Hydrodesulfurization of Benzothiophene Catalyzed by Molybdenum Sulide Cluster Encapsulatcd into Zeolites" Studies in Surface Science and Catalysis. 101. 107-116 (1996)

M.Taniguchi、S.Yasuda、Y.Isii、I.Murata、M.Hidai、T.Tatsumi：“封装在沸石中的硫化钼簇催化苯并噻吩的加氢脱硫”表面科学和催化研究。

T.Tatsumi: "Zeolite-Supported Hydrodesulfurization Catalysts Prepared by Ion exchange with Mo and Mo-Ni Sulfide Clusters" Appl.Catal.,A. 139. L5-L10 (1996)

T.Tatsumi：“通过与Mo和Mo-Ni硫化物团簇进行离子交换制备的沸石支持的加氢脱硫催化剂”Appl.Catal.，A。

T.Tatsumi, M.Taniguchi, H.Ishige, Y.Ishii, T.Murata, M.Hidai: "Effectiveness of Mo-Ni sulfide clusters in the preparation of zeolite-supported hydrodcsulfurization catalysts" Applied Surface Science. 121/122. 500-504 (1997)

T.Tatsumi、M.Taniguchi、H.Ishige、Y.Ishii、T.Murata、M.Hidai：“Mo-Ni 硫化物簇在沸石负载加氢脱硫催化剂制备中的有效性”应用表面科学。

M.Taniguchi, S.Yasuda, Y.Ishii, T.Murata, M.Hidai, T.Tatsumi: "Hydrodesulfurization of Benzothiophene Catalyzed by Molybdenum Sulide Cluster Encapsulated into Zeolites" Studies in Surface Science and Catalysis. 101. 107-116 (1996)

M.Taniguchi、S.Yasuda、Y.Ishii、T.Murata、M.Hidai、T.Tatsumi：“封装在沸石中的硫化钼簇催化苯并噻吩的加氢脱硫”表面科学和催化研究。