Development of radioactive ^<35>S and ^3H pulse tracer methods-Elucidation of behaviors of sulfur and hydrogen on sulfided catalysts

放射性^<35>S和^3H脉冲示踪方法的发展-硫和氢在硫化催化剂上的行为的阐明

• 批准号: 08455371
• 负责人: KABE Toshiaki
• 金额: $ 5.25万
• 依托单位: Tokyo University of Agriculture and Technology
• 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-08455371/
• 关键词: radioactive tracer method; Hydrodesulfurization; Sulfur behavior; Labile sulfur; Structure of sulfided catalysts; Hydrogen behavior; Hydrodesulfurization mechanism; Deep hydrodesulfurization of light gas oil; 触媒; 水素化; 脱硫; 石炭液化; ラジオアイソトープトレーサー法

This research was supported by grants from the Ministry of Education, Science, Sports and Culture as Grant-in-Aid for Scientific Research (B) (2) with the project number 08455371 in the two years (1996-1997). This report summarized the study results on the structure of sulfided catalysts and the mechanism of deep hydrodesulfurization of a light gas oil using ^<35>S and ^3H radioisotope pulse tracer methods. Many basic point on the structure of HDS catalyst and the mechanism have still remained to be clarified although a number of studies on elucidation of HDS mechanisms using conventional characterization technique and the kinetic analysis method were reported. Especially, there have been few examples clarifying the behavior of sulfur on the working-catalyst. In order to develop the new catalysts continuously, it is essential to know in more detail the hydrodesulfurization mechanism. On the other hand, the tracer method has been considered to enable us quantify the behavior of sulfur o … More n the working catalyst and hydrogen behavior in the practical hydrodesulfurization reaction. Therefore, in this study, a ^<35>S and ^3H radioisotope pulse tracer method was developed and was applied to several aspects as follows : 1) Presulfidation mechanism of No-based desulfurization catalysts ; 2) Hydrodesulfurization kinetics of dibenzothiophenes on Mo-based catalysts ; 3) Retarding effect of H_2S and solvent on hydrodesulfurization reaction ; 4) Elucidation of sulfur mobility on Mo-based catalysts in hydrodesulfurization by ^<35>S pulse tracer method : 5) Deep desulfurization mechanism of light gas oil ; 6) Novel desulfurization catalysts using supported metal carbonyl complexes as catalytic precursors. From these studies, a lot of new information on the structure of sulfided catalysts, the insight of active sites and the mechanism of hydrodesulfurization was obtained. This makes us gain a good deal of enlightenment for development of new catalysts appropriated to the dep hydrodesulfurization of light gas oil. Less

这项研究得到了教育、科学、体育和文化部作为科学研究补助金（B）（2）的赠款，项目号为08455371，为期两年（1996-1997年）。本文总结了用~（13）S和~（13）H放射性同位素脉冲示踪法对硫化催化剂结构和轻质柴油深度加氢脱硫机理的研究结果<35>。尽管用常规表征技术和动力学分析方法对HDS机理进行了大量的研究，但对HDS催化剂的结构和机理的许多基本观点仍有待澄清。特别是，很少有实例阐明硫在工作催化剂上的行为。为了不断开发新的催化剂，有必要更详细地了解加氢脱硫机理。另一方面，示踪剂方法已被认为使我们能够量化硫的行为， ...更多信息 在实际加氢脱硫反应中的氢行为。因此，本研究建立了一种~（13）<35>S和~（13）H同位素脉冲示踪法，并将其应用于以下几个方面：1）NO基脱硫催化剂的预硫化机理; 2）二苯并噻吩在Mo基催化剂上的加氢脱硫动力学; 3）H_2S和溶剂对加氢脱硫反应的阻滞作用; 4）~（13）S脉冲示踪法研究Mo基催化剂上硫的迁移<35>方法：5）轻柴油深度脱硫机理; 6）以负载型金属羰基络合物为催化前驱体的新型脱硫催化剂。通过这些研究，在硫化催化剂的结构、活性中心和加氢脱硫机理等方面获得了许多新的信息。这对开发适合于轻质柴油深度加氢脱硫的新型催化剂有很好的启示。少

项目成果

A.Ishihara, M.Nomura, K.Shirouchi, and T.Kabe: "Hydrodesulfurization of Dibenzothiophene Catalyzed by Supported Metal Carbonyls Complexes (Part 6). Effect of Supports on Activities of HDS Catalysts Prepared from Supported Ruthenium Carbonyl-Cesium Hydrode

A.Ishihara、M.Nomura、K.Shirouchi 和 T.Kabe：“负载型金属羰基配合物催化二苯并噻吩的加氢脱硫（第 6 部分）。载体对负载型羰基铯氢化物制备的 HDS 催化剂活性的影响

Q.Zhang, W.Qian, S.Oshima, A.Ishihara, and T.Kabe: "The Role of Cobalt on Hydrodesulfurization and Hydrogenation of Dibenzo-thiophene and 4,6-Dimenthyl-dibenzothiophene Catalyzed Co-Mo/Al_2O_3" J.Jpn.Petrol, Inst.(Sekiyu Gakkaishi). 40(5). 408-414 (1997)

Q.Zhang、W.Qian、S.Oshima、A.Ishihara 和 T.Kabe：“钴对二苯并噻吩和 4,6-二薄荷基二苯并噻吩催化 Co-Mo/Al_2O_3 加氢脱硫和氢化的作用”J

W,Qian, A.Ishihara, G.Wang, T.Tsuzuki, M.Godo, and T.Kabe: "Elucidation of Behavior of Sulfur on Sulfided Co-Mo/Al_2O_3 Catalysts Using a ^<35>S Radioisotope Pulse Tracer Method" J.Catal.170. 286-294 (1997)

W,Qian, A.Ishihara, G.Wang, T.Tsuzuki, M.Godo, and T.Kabe：“使用 ^<35>S 放射性同位素脉冲示踪法阐明硫在硫化 Co-Mo/Al_2O_3 催化剂上的行为

W.Qian: "Elucidation of Molybdenum-based Catalysts Using a Radioisotope Tracer Method (Part1) Hydrodesulfurization Activitly and siucture of Sulfided Molybdena-Alumina Cal" J.Chem.Soc.Faraday Trans. 93. 1821-1826 (1997)

W.Qian：“利用放射性同位素示踪法阐明钼基催化剂（第一部分）加氢脱硫活性和硫化钼-氧化铝钙的结构”J.Chem.Soc.Faraday Trans。

T.Kabe: "Elucidation of Hydrodesulfurization Meehanism Using ^<35>S Redioisotope Pulse Traeer Methods" Catalysis Today. 1107. 1-10 (1997)

T.Kabe：“利用^ 35 S重碘同位素脉冲追踪方法阐明加氢脱硫机制”今日催化。