Reaction Mechanism of Carbon-Carbon Bond Formation on Zeolite Catalyst

• Project/Area Number: 09440248
• Research Category: Grant-in-Aid for Scientific Research (B).
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 物質変換
• Research Institution: National Science Museum
• Principal Investigator: WAKABAYASHI Fumitaka National Science Museum, Department of Science and Engineering, Senior Curator, 理工学研究部, 主任研究官 (30158589)
• Project Period (FY): 1997 – 2000
• Project Status: Completed (Fiscal Year 2000)
• Budget Amount: ¥14,000,000 (Direct Cost: ¥14,000,000); Fiscal Year 2000: ¥1,700,000 (Direct Cost: ¥1,700,000); Fiscal Year 1999: ¥1,600,000 (Direct Cost: ¥1,600,000); Fiscal Year 1998: ¥3,300,000 (Direct Cost: ¥3,300,000); Fiscal Year 1997: ¥7,400,000 (Direct Cost: ¥7,400,000)
• Keywords: 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

Research Abstract

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.

Research Products

• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "IR study of adsorption and reaction of 1-butene on H-ZSM-5"Catalysis Letters. 47. 129-133 (1997)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Double bond migration of an olefin without protonated species on H (D) form zeolites"The Journal of Physical Chemistry B. 101. 9314-9320 (1997)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "IR study of adsorption of olefins on deuterated ZSM-5"The Journal of Physical Chemistry B. 102. 2259-2262 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Double bond migration of 1-butene without protonated intermediated on D-ZSM-5"Microporpous and Mesoprous Materials. 21. 429-437 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "IR study of reaction of 2-butene adsorbed on deuterated ZSM-5 and mordenite"Catalysis Letters. 53. 215-220 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Byongjin Lee et al.: "Infrared spectroscopic study of high temperature behavior of the Bronsted acidic hydrozyl groups on zeolites"Bulletin of Chemical Society of Japan. 71. 2149-2152 (1998)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Byongjin Lee et al.: "FT-IR study of H_2^<16>O and H_2_<18>O adsorption on H-ferrierite"Journal of Molecular Catalysis A : Chemical. 137. 269-272 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Fumitaka Wakabayashi et al.: "FT-IR study of the reactivity of the surface methoxy species formed by the reaction of methanol on H-ZSM-5"Proceedings of the 12th International Zeolite Conference, Baltimore, USA, July 5-10,1998. 2577-2584 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Structure of dimerized alkoxy species of 2-methylpropene on zeolites and silica-alumina studied by FT-IR"The Journal of Physical Chemistry B. 103. 8538-8543 (1999)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Acid property of silanol groups on zeolites assessed by reaction probe IR study"Journal of Catalysis. 191. 275-281 (2000)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Unusual isomerization routes of η-butenes on the acidic OH (OD) groups on ferrierite zeolite studied by FT-IR"Studies in Surface Science and Catalysis. 130C. 2933-2938 (2000)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] J.N.Kondo et al.: "Migration of butene isomers onto the acidic OH groups in small micropores of ferrierite"Catalysis Today. 63. 305-308 (2000)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Junko N.Kondo, Kazunari Domen, Fumitaka Wakabayashi.: "A novel route of double bond migration of an olefin without protonated species on ZSM-5 zeolite."The Journal of Physical Chemistry B. Vol.101, No.28. 5477-5479 (1997)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] J.N.Kondo, S.Liqun, K.Domen, F.Wakabayashi.: "IR study of adsorption and reaction of 1-butene on H-ZSM-5."Catalysis Letters. Vol.47, No.2. 129-133 (1997)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Shao Liqun, Fumitaka Wakabayashi, Kazunari Domen.: "Double bond migration of an olefin without protonated species on H(D) form zeolites."The Journal of Physical Chemistry B. Vol.101, No.45. 9314-9320 (1997)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Kazunari Domen, Fumitaka Wakabayashi.: "IR study of adsorption of olefins on deuterated ZSM-5."The Journal of Physical Chemistry B. Vol.102, No.12. 2259-2262 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Kazunari Domen, Fumitaka Wakabayashi.: "Double bond migration of 1-butene without protonated intermediate on D-ZSM-5."Microporous and Mesoporous Materials. Vol.21, No.4-6. 429-437 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Fumitaka Wakabayashi, Kazunari Domen.: "IR study of reaction of 2-butene adsorbed out deuterated ZSM-5 and mordenite."Catalysis Letters.. Vol.53, No.3-4. 215-220 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Byongjin Lee, Junko N.Kondo, Fumitaka Wakabayashi, Kazunari Domen.: "Infrared spectroscopic study of high temperature behavior of the Bronsted acidic hydroxyl groups on zeolites."Bulletin of Chemical Society of Japan. Vol.71, No.9. 2149-2152 (1998)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Byongjin Lee, Junko N.Kondo, Kazunari Domen, Fumitaka Wakabayashi.: "FT-IR study of H_2^<16>O and H_2^<18>O adsorption on H-ferrierite."Journal of Molecular Catalysis A : Chemical. Vol.137, No.1-3. 269-272 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] F.Wakabayashi, J.N.Kondo, C.Hirose, K.Domen.: "FT-IR study of the reactivity of the surface methoxy species formed by the reaction of methanol on H-ZSM-5."Proceedings of the 12th International Zeolite Conference, Baltimore, USA, July 5-10, 1998. 2577-2584 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Byongjin Lee, Junko N.Kondo, Kazunari Domen, Fumitaka Wakabayashi.: "Infrared study of H/D isotope exchange reaction of alkanes and Bronsted acidic hydroxyl groups on FER zeolite."Catalysis Letters. Vol.59, No.1. 51-54 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Ishikawa, Eisuke Yoda, Junko N.Kondo, Fumitaka Wakabayashi, Kazunari Domen.: "Stable dimerized alkoxy species of 2-methylpropene on mordenite zeolite studied by FT-IR."The Journal of Physical Chemistry B. Vol.103, No.27. 5681-5686 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Hiroyuki Ishikawa, Eisuke Yoda, Fumitaka Wakabayashi, Kazunari Domen.: "Structure of dimerized alkoxy species of 2-methylpropene on zeolites and silica-alumina studied by FT-IR."The Journal of Physical Chemistry B. Vol.103, No.40. 8538-8543 (1999)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Eisuke Yoda, Junko N.Kondo, Fumitaka Wakabayashi, Kazunari Domen.: "Shape selective adsorption of olefins on Bronsted acidic OH (OD) groups on ferrierite studied by FT-IR."Applied Catalysis A. Vol.194-195, No.1-2. 275-283 (2000)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Eisuke Yoda, Hiroyuki Ishikawa, Fumitaka Wakabayashi, Kazunari Domen.: "Acid property of silanol groups on zeolites assessed by reaction probe IR study."Journal of Catalysis. Vol.191, No.2. 275-281 (2000)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Eisuke Yoda, Fumitaka Wakabayashi, Kazunari Domen.: "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.. Vol.130, Part C. 2933-2938 (2000)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Junko N.Kondo, Eisuke Yoda, Fumitaka Wakabayashi, Kazunari Domen: "Migration of butene isomers onto the acidic OH groups in small micropores of ferrierite."Catalysis Today. Vol.63, No.2-4. 305-308 (2000)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] H.Ishikawa et al.: "Stable dimerized alkoxy species of 2-methylpropene on mordenite zeolite studied by FT-IR."Journal of Physical Chemistry B. 103・27. 5681-5686 (1999)
• [Publications] J.N.Kondo et al.: "Structure of dimerized alkoxy species of 2-methylpropene on zeolites and silica-alumina studied by FT-IR."Journal of Physical Chemistry B. 130・40. 8538-8543 (1999)
• [Publications] E.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・1-2. 275-283 (2000)
• [Publications] J.N.Kondo et al.: "Acid property of silanol groups on zeolites assessed by reaction probe IR study."Journal of Catalysis. 191・2. 275-281 (2000)
• [Publications] 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)
• [Publications] J.N.Kondo et al.: "Migration of butene isomers onto the acidic OH groups in small micropores of ferrierite."Catalysis Today. 63・2-4. 305-308 (2000)
• [Publications] F. Wakabayashi: "FT-IR study of the reactivity of the surface methoxy species formed by the reaction of methanol on H-ZSM-5"Proceedings of the 12th International Zeolite Conference, Baltimore, USA, July 5-10, 1998. IV. 2577-2584 (1999)
• [Publications] B. Lee: "FT-IR Study of H_2^<16>O and H_2^<18>O adsorption on H-ferrierite"J. Mol. Catal. A. 137・1-3. 269-272 (1999)
• [Publications] B. Lee: "Infrared study of H/D isotope exchange reaction of alkanes and Bronsted acidic hydroxyl groups in FER Zeolete"Catal. Lett.. 59・1. 51-54 (1999)