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

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)的赠款的支持，两年(1996年至1997年)项目编号为08455371。本文总结了用S和~3H放射性同位素脉冲示踪法对轻柴油硫化催化剂结构和深度加氢脱硫机理的研究结果。关于加氢脱硫催化剂的结构和反应机理的许多基本观点仍有待阐明，尽管已报道了一些利用常规表征技术和动力学分析方法阐明加氢脱硫反应机理的研究。特别是，阐明硫在工作催化剂上的行为的例子很少。为了不断开发新的催化剂，有必要更详细地了解加氢脱硫的机理。另一方面，示踪方法被认为可以使我们定量测定硫磺o…的行为。在实际的加氢脱硫反应中，更多地考虑了工作催化剂和氢气行为。为此，本研究发展了放射性同位素脉冲示踪法，并将其应用于如下几个方面：1)NO基脱硫催化剂的预硫化机理；2)二苯并噻吩类化合物在钼系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抑制作用；4)研究钼系催化剂加氢脱硫中硫的活动性。通过这些研究，对硫化催化剂的结构、活性中心和加氢脱硫机理等方面获得了许多新的信息。这对开发适用于轻柴油深度加氢脱硫的新型催化剂有很大的启示。较少

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