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.

我们打算通过利用沸石的酸度来促进二甲基二苯甲酸烯的氢化硫化反应性，特别是4,6-二甲基苯二甲酸酯，尤其是利用沸石的酸度，从而促进脱甲基化或甲基化反应。我们已经成功地掺入了硫化钼簇，[MO_3S_4（H_2O）_9]^<4+>具有不完全的Cubane型结构，而钼nickel-nickel群集则具有完整的Cubane型结构，可通过含水环交换为12-C-ember seplites Zeolites。还可以通过用铵己酸铵和硝酸盐的溶液浸入AL_2O_3来制备控制催化剂MO/AL_2O_3和MONI/AL_2O_3。在制备MO/KL和Mo-Mor时，发现离子交换迟钝，交换程度低至20％。然而，尽管钼负载较低，但MO/KL比MO/NAY表现出比MO/NAY更高的HDS活性。 NI的参与导致HDS活性的大大增强。但是，与NIS-MOS_2/AL_2O_3 Catalyst相比，MONI/KL在苯甲苯二苯的HDS的活性较小。相比之下，MONI/KL比NIS-MOS_2/AL_2O_3催化剂显示出4,6-二甲基苯甲酸噻吩的HDS的活性更高。从对产物分布的分析中，可以得出结论，MONI/KL的高活性是由于反应物通过脱甲基化或通过催化剂酸度促进的甲基化或甲基转移反应的转化而引起的。

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。

T.Tatsumi, M.Taniguchi, S.Yasuda, Y.Ishii, T.Murata, M.Hidai: "Zeolite-supported hydrodesulfurization catalysts prepared by ion exchange with 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。