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.

我们打算通过分子筛的酸性来促进脱甲基或甲基转移反应，从而提高二甲基二苯并硫苯，特别是4，6-二甲基二苯并硫苯的加氢脱硫活性。通过水溶液离子交换，我们成功地将不完全立方烷型结构的硫化钼簇合物[Mo_3S_4(H_2O)_9]和完全立方烷型结构的钼镍簇合物引入到沸石分子筛中。用七钼酸铵和硝酸镍溶液浸渍Al_2O_3，然后预硫化，制备了Mo/Al_2O_3和MoNi/Al_2O_3对照催化剂。在制备Mo/KL和Mo-MoR时，发现离子交换反应迟缓，交换度低至20%。然而，尽管Mo/KL和Mo/NaY催化剂的钼负载量较低，但其HDS活性仍高于Mo/NaY催化剂。Ni的加入大大提高了催化剂的加氢脱硫活性，但MoNi/KL催化剂的加氢脱硫活性低于NiS-MoS2/Al_2O_3催化剂。与NiS-MoS_2/Al_2O_3催化剂相比，MoNi/KL催化剂对4，6-二甲基苯并噻吩加氢反应表现出更高的催化活性。对产物分布的分析表明，MoNi/KL的高活性是由于催化剂的酸性促进了反应物的脱甲基化或甲基转移反应，从而使反应物转化为更具活性的反应物。

项目成果

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, 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。

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。