Activation Mechanism of Hydrogen and Organosulfur Compounds over Supported Noble Metal Hydrodesulfurization Catalysts

负载型贵金属加氢脱硫催化剂上氢和有机硫化合物的活化机理

• 批准号: 14550757
• 负责人: SUGIOKA Masatoshi
• 金额: $ 2.11万
• 依托单位: MURORAN INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550757/
• 关键词: Noble metal; Mesoporous silica; Desulfurization catalyst; Hydrogen; Thiophene; Activation mechanism; Reaction mechanism; Catalyst design; 活性化; 反応機構

The order of noble metals (MM) supported on mesoporous silica MCM-41 for the hydrodesulfurization (HDS) of thiophene at 350℃ was Pt>Pd>Rh>>Ru. This order is corresponded to that of n-butane formation in the HDS of thiophene, indicating that hydrogen is activated on MM to form spillover hydrogen.On the other hand, thiophene is activated on silanol groups (Si-OH) on MCM-41. The spillover hydrogen formed on NM attacks the thiophene molecule activated on MCM-41 in the HDS of thiophene. These results suggested that the high dispersion of NM on MCM-41 to form spillover hydrogen and the enhancement of surface acidity of MCM-41 is important in order to design highly active NM/MCM-41 catalysts for the HDS reaction. The surface modification of MCM-41 with alumina was performed to enhanced the acidity of MCM-41 and the NM dispersion on MCM-41. The catalytic activity of NM, especially Pt, supported on Al_2O_03 modified MCM-41 (Pt/Al_2O_3-MCM-41) for the HDS of thiophene was remarkably higher than Pt/MCM-41. In this work, new highly active Pt/Al_2O_3-MCM-41 catalyst has been successfully developed for the HDS of organosulfur compounds contained in the petroleum feedstocks.

介孔二氧化硅MCM-41负载噻吩350℃加氢脱硫过程中贵金属的顺序为Pt>Pd>Rh>>Ru。这个顺序与噻吩HDS中正丁烷的生成顺序一致，说明氢在MM上被活化形成外溢氢。另一方面，噻吩在MCM-41的硅醇基（Si-OH）上被活化。NM上形成的溢出氢攻击噻吩HDS中MCM-41上活化的噻吩分子。这些结果表明，纳米在MCM-41上的高度分散形成溢出氢和提高MCM-41的表面酸度是设计高活性纳米/MCM-41 HDS反应催化剂的重要因素。采用氧化铝对MCM-41进行表面改性，提高了MCM-41的酸性和纳米粒子在MCM-41上的分散性能。在Al_2O_03改性MCM-41 （Pt/Al_2O_3-MCM-41）上负载NM，尤其是Pt对噻吩HDS的催化活性显著高于Pt/MCM-41。本文成功研制了新型高效Pt/Al_2O_3-MCM-41催化剂，用于石油原料中含有机硫化合物的HDS。

项目成果

M.Sugioka, T.Kurosaka: "Catalytic activities of noble metals supported on zeolites and related materials for the hydrodesulfurization of thiophenes"Journal of Japan Petroleum Institute. 46(6). 342-354 (2002)

M.Sugioka，T.Kurosaka：“沸石和相关材料负载的贵金属对噻吩加氢脱硫的催化活性”日本石油学会杂志。

M.Sugioka 他: "Catalytic performance of noble metals supported on Al_2O_3-modified mesoporous silica MCM-41 for thiophene hydrodesulfurization"Journal of Japan Petroleum Institute. (発表予定).

M. Sugioka等：“Al_2O_3改性介孔二氧化硅MCM-41负载贵金属对噻吩加氢脱硫的催化性能”，日本石油学会学报（待出版）。

M.Sugioka, T.Aizawa, Y.kanda, T.Kurosaka, Y.Uemichi, S.Namba: "Catalytic performance of mesoporous silica SBA-15-supported noble metals for thiophene hydrodesulfurization"Studies in Surface Science and catalysis. 142. 739-746 (2002)

M.Sugioka、T.Aizawa、Y.kanda、T.Kurosaka、Y.Uemichi、S.Namba：“介孔二氧化硅 SBA-15 负载的贵金属用于噻吩加氢脱硫的催化性能”表面科学和催化研究。

M.Sugioka 他: "Catalytic performance of mesoporous silica SBA-15 -supported noble metals for thiophene hydrodesulfurization"Studies in Surface Science and Catalysis. 142. 739-746 (2002)

M.Sugioka 等：“介孔二氧化硅 SBA-15 负载的贵金属用于噻吩加氢脱硫的催化性能”表面科学与催化研究 142. 739-746 (2002)。

杉岡正敏 他: "金属酸化物担持貴金属系触媒によるチオフェンの水素化脱硫反応"石油学会誌. (発表予定).

Masatoshi Sugioka 等人：“使用金属氧化物负载的贵金属催化剂进行噻吩的加氢脱硫反应”，日本石油学会杂志（预定发表）。