Reaction Mechanism of Carbon-Carbon Bond Formation on Zeolite Catalyst

沸石催化剂上碳-碳键形成的反应机理

• 批准号: 09440248
• 负责人: WAKABAYASHI Fumitaka
• 金额: $ 8.96万
• 依托单位: National Science Museum
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-09440248/
• 关键词: zeolite; acid site; acidic hydroxy group; infrared spectroscopy; MTG reaction; alkene; isomerization; フェリエライト; 触媒作用; 反応機構; オレフィン; MTGプロセス; 拡散反射法; ジメチルエーテル; メトキシ種

IR studies were carried out to elucidate the reaction mechanism of the carbon-carbon bond formation that is one of the most important reactions of zeolite catalysis. Reactivity and adsorption structure of olefins on zeolites were also investigated.(1) Reactivity of methoxy species formed by the reaction of methanol on Zeolites :Three sorts of methoxy species were formed on zeolite by the reaction of methanol in the temperature range between 140 and 240℃. It was observed that dimethyl ether was formed by the reaction of these methoxy species and methanol,(2) Acid properties of hydroxyl groups on zeolites :Behavior of acidic OH groups on zeolites at higher temperature was examined by IR spectroscopy in situ. Adsorption structure of water on ferrierite that has small cages was also examined.(3) Adsorption of olefins on zeolites :It was observed that olefins were selectively adsorbed on active sites on ferrierite that has small cages. The change of the adsorption structure with the change of the adsorption temperature was also studied.(4) Double bond migration of olefins on zeolites :It was found that double bond of olefins migrated without forming protonated species in the low temperature range.(5) The structure and reactivity of the alkoxy species formed by the adsorption of olefins on zeolites :Dimerized alkoxy species were observed for the adsorption of isobutene on zeolites above 200 K.(6) H/D exchange reaction of olefins on zeolites :The H/D exchange reaction between olefins and hydroxy groups on zeolites was studied.

碳-碳键形成反应是分子筛催化的重要反应之一。研究了烯烃在分子筛上的反应活性和吸附结构。(1)甲醇在沸石上反应生成甲氧基物种的反应性：甲醇在140 ~ 240℃温度范围内在沸石上反应生成三种甲氧基物种。（2）分子筛上羟基的酸性：用原位红外光谱研究了分子筛上酸性羟基在高温下的行为。水在具有小笼状结构的镁碱沸石上的吸附结构也进行了研究。(3)烯烃在沸石上的吸附：观察到烯烃选择性地吸附在具有小笼的镁碱沸石上的活性位点上。研究了吸附温度对吸附结构的影响。(4)烯烃在分子筛上的双键迁移：发现在低温范围内，烯烃的双键发生迁移而不形成质子化物种。(5)烯烃在沸石上吸附形成的烷氧基物种的结构和反应性：在高于200 K的温度下，异丁烯在沸石上吸附时，观察到二聚烷氧基物种。(6)烯烃在分子筛上的H/D交换反应：研究了烯烃与分子筛上羟基之间的H/D交换反应。

项目成果

J.N.Kondo et al.: "Unusual isomerization routes of n-butenes on the acidic OH (OD) groups on ferrierite zeolite studied by FT-IR."Studies in Surface Science and Catalysis. 130・C. 2933-2938 (2000)

J.N.Kondo 等人：“通过 FT-IR 研究镁碱沸石上酸性 OH (OD) 基团上的正丁烯的异常异构化路线。”表面科学与催化研究 130・C。

Byongjin Lee et al.: "Infrared study of H/D isotope exchange reaction of alkanes and Bronsted acidic hydroxyl groups on FER zeolite"Catalysis Letters. 59. 51-54 (1999)

Byongjin Lee等：“FER沸石上烷烃和布朗斯台德酸性羟基的H/D同位素交换反应的红外研究”催化快报。

J.N.Kondo et al.: "A novel route of double bond migration of an olefin without protonated species on ZSM-5 zeolite"The Journal of Physical Chemistry B. 101. 5477-5479 (1997)

J.N.Kondo 等人：“ZSM-5 沸石上无质子化物质的烯烃双键迁移的新途径”物理化学杂志 B. 101. 5477-5479 (1997)

Hiroyuki Ishikawa et al.: "Stable dimerized alkoxy species of 2-methylpropene on mordenite zeolite studied by FT-IR"The Journal of Physical Chemistry B. 103. 5681-5686 (1999)

Hiroyuki Ishikawa 等人：“通过 FT-IR 研究丝光沸石上 2-甲基丙烯的稳定二聚烷氧基”物理化学杂志 B. 103. 5681-5686 (1999)

Eisuke Yoda et al.: "Shape selective adsorption of olefins on Bronsted acidic OH (OD) groups on ferrierite studied by FT-IR"Applied Catalysis A. 194-195. 275-283 (2000)

Eisuke Yoda 等人：“通过 FT-IR 研究镁碱沸石上布朗斯台德酸性 OH (OD) 基团上烯烃的形状选择性吸附”应用催化 A. 194-195。