超臨界流体を反応場とする固体酸触媒プロセスの環境負担性削減に関する研究

2008 Fiscal Year Annual Research Report

• Project/Area Number: 19310060
• Research Institution: Gifu University
• Principal Investigator: 杉 義弘 Gifu University, 工学部, 教授 (90281047)
• Co-Investigator(Kenkyū-buntansha): 小村 賢一 岐阜大学, 工学部, 准教授 (40377685)
• Keywords: ゼオライト / メソポーラス材料 / 超臨界媒体 / 炭酸ガス / ナノサイズベータゼオライト / 形状選択性

Research Abstract

環境調和型化学プロセスの鍵技術である超臨界流体、特に超臨界炭酸ガス(sc-CO_2)媒体中における固体酸塩基触媒機能を検討した。また、新規触媒機能を有する多孔質の創成に関する研究を行った。
1.sc-CO_2のゼオライト触媒反応への適用の可能性をH-モルデナイトによるイソブチルベンゼンのイソプロピル化における形状選択性を検討した。sc-CO_2中では通常の窒素雰囲気下におけるより高い触媒活性が観測された。この際反応後の触媒中に存在する炭素質の量が著しく少ないことより、触媒の不活性化の原因になる炭素質がsc-CO_2により除去されると考えられた。この際、4-イソブチルクメンが80%以上の選択率で得られ、モルデナイトはsc-CO_2中でも形状選択性を示すことが明らかになった。ナフタレン及びビフェニルのイソプロピル化においても同様の間素質現象が認められた。
2.sc-CO_2中でも安定なゼオライト骨格を有するメソポーラス材料の合成を行った。ゼオライト骨格を導入するために水酸化テトラエチルアンモニウム(TEAOH)、メソポーラス構造を導入するために、臭化セチルトリメチルアンモニウム(CTMABr)を用い120℃で加熱することにより、ベータゼオライト骨格を有するメソポーラス材料Al-MCM-48-SUBの合成に成功した。HP-Xe-NMRよりゼオライト骨格及びメソポーラス孔の二種類の細孔が存在することが明らかになった。
3.ベータゼオライトのナノサイズ化に関する検討を行うために、ベータゼオライトが生成することが知られているSDAであるTEAOHに界面活性剤であるCTMABrの添加効果を検討し、適量のTEAOHにより30-100nmの均一なべータゼオライト結晶を得た(合成温度を175℃に設定した)。本ゼオライトの外表面酸点の触媒機能を評価するために、1-オクテンのアルキル化をsc-CO_2媒体中で行い、粒子径と反応活性が反比例することがわかった。このことは外表面酸点の有効性を示すものである

Research Products

• [Journal Article] Highly stable Mesoporous Aluminosilicates with a Dual Pore System : Simultaneous Formation of Mesophase with Zeolitic Building Units (2009)
  • Author(s): S. C. Laha, A. Sakthivel, K. Komura, S. -J. Huang, P. -H. Wu, S. -B. Liu, Y. Sasaki, M. Kobayashi, Y. Sugi
  • Journal Title: Chem. Lett. 38(印刷中)
  • Peer Reviewed
• [Journal Article] The Isomerization of 4, 4'-Diisopropylbiphenyl at External Acid Sites in the Isopropylation of Biphenyl over H-Mordenites (2009)
  • Author(s): Y. Sugi, I. Toyama, H. Tamada, S. Tawada, K. Komura, Y. Kubota
  • Journal Title: J. Mol. Catal. A : Chemical 304 Pages: 22-27
  • Peer Reviewed
• [Journal Article] The β-Zeolite Synthesized by Dry-gel Conversion Method Without the Use of Sodium Hydroxide : Characterization and Catalytic Behaviors (2009)
  • Author(s): T. Shibata, S. Suzuki, H. Maekawa, K. Komura, Y. Kubota, Y. Sugi
  • Journal Title: J. Mol. Catal. A : Chemical 297 Pages: 80-85
  • Peer Reviewed
• [Journal Article] The β-Zeolite Synthesized by Dry-gel Conversion Method without the Use of Sodium Hydroxide : Characterization and Catalytic Behaviors (2009)
  • Author(s): A. Sakthivel, A. Iida, K. Komura, Y. Sugi
  • Journal Title: J. Nanosci. Nanotechnol. 9 Pages: 475-483
  • Peer Reviewed
• [Journal Article] Nano-sized β-Zeolites with Tunable Particle Sizes : Synthesis by DGC Method in the Presence of Surfactants, Characterization, and Catalytic Properties (2009)
  • Author(s): A. Sakthivel, A. Iida, K. Komura, Y. Sugi, K. V. R. Chary
  • Journal Title: Micorpor. Mesopor. Mater. 119 Pages: 322-330
  • Peer Reviewed
• [Journal Article] Na-Y Zeolite as a Highly Active Catalyst for the Hydroamination of α, β-Unsaturated Compounds with Aromatic Amines (2009)
  • Author(s): K. Komura, R. Hongo, J. Tsutsui, Y. Sugi
  • Journal Title: Catal. Lett. 128 Pages: 203-209
  • Peer Reviewed
• [Journal Article] Strong Acids as Catalysts for the Chloromethylation of m-Xylene. Environmentally Conscious Synthesis of 1, 3-bis(Chloromethyl)-4, 6-dimethylbenzene (2009)
  • Author(s): T. Kishida, N. Ieda, T. Yamauchi, K. Komura, Y. Sugi
  • Journal Title: Ind. Eng. Chem. Res. 48 Pages: 1831-1839
  • Peer Reviewed
• [Journal Article] Tungstophosphoric Acid Supported on MCM-48 : An Efficient Catalyst for the Esterification of Long Chain Fatty Acids and Alcohols in Supercritical Carbon Dioxide (2009)
  • Author(s): A. Sakthivel, K. Komura, Y. Sugi
  • Journal Title: Ind. Ens. Chem. Res. 47 Pages: 2538-2544
  • Peer Reviewed
• [Journal Article] The Alkylation of Naphthalene over One-dimensional Twelve-membered Ring Zeolites. The Influence of Zeolite structure and Alkylating Agents on the Selectivity for Dialkylnaphthalenes (2009)
  • Author(s): Y. Sugi, H. Maekawa, H. Naiki, K. Komura, Y. Kubota
  • Journal Title: Bull. Chem. Soc. Jpn. 81 Pages: 897-905
  • Peer Reviewed
• [Journal Article] The Isopropylation of Biphenyl over One-dimensional Zeolites with Corrugated Channels (2008)
  • Author(s): H. Maekawa, T. Shibata, A. Niimi, C. Asaoka, K. Yamasaki, H Naiki, K. Komura, Y. Kubota, Y. Sugi, J. -Y. Lee, J. -H. Kim, G. Seo
  • Journal Title: J. Mol. Catal. A : Chemical 279 Pages: 27-36
  • Peer Reviewed
• [Journal Article] The Alkylation of Biphenyl over Three-Dimensional Large Pore Zeolites. The Influence of Zeolite structure and Alkylating Agents on the Selectivity for 4, 4' -Dialkylbiphenyl (2008)
  • Author(s): Y. Sugi, H. Maekawa, Y. Hasegawa, A. Ito, R. Asai, D. Yamamoto, K. Komura, Y. Kubota, J. -H. Kim, G. Seo
  • Journal Title: Catal. Today 131 Pages: 413-422
  • Peer Reviewed
• [Journal Article] The Esterification of Glycerine with Laurie Acid Catalyzed by Multi-valent Metal Salts. Selective Formation of Mono-and Dilaurins (2008)
  • Author(s): R. Nakamura, K. Komura, Y. Sugi
  • Journal Title: Catal. Commun. 9 Pages: 511-515
  • Peer Reviewed
• [Journal Article] Fe (III) Containing Mesoporous Molecular Sieves with Framework Zeolite Secondary Building Units (2008)
  • Author(s): A. Sakthivel, K. Komura, Y. Sugi
  • Journal Title: J. Nanosci. Nanotechnol. 8 Pages: 400-404
  • Peer Reviewed
• [Journal Article] The Alkylation of Naphthalene over Three-dimensional Large Pore Zeolites. The Influence of Zeolite Structure and Alkylating Agent on the Selectivity for Dialkylnaphthalenes (2008)
  • Author(s): Y. Sugi, H. Maekawa, Y. Hasegawa, H. Naiki, K. Komura, Y. Kubota
  • Journal Title: Catal. Today 132 Pages: 27-37
  • Peer Reviewed
• [Journal Article] The Shape-selective Ethylation of Biphenyl over H-Mordenite. Reactivity of the Intermediates on the Catalysis (2008)
  • Author(s): Y. Sugi, S. Watanabe, Y. Imada, K. Komura, Y. Kubota
  • Journal Title: J. Mol. Catal. A : Chemical 285 Pages: 101-110
  • Peer Reviewed
• [Journal Article] Selective Isopropylation of Isobutylbenzene over H-Mordenite in Supercritical C0_2 Medium : Remarkable Enhancement in Catalytic Activity and Selectivity for 4-Isobutylcumene (2008)
  • Author(s): S. C. Laha, K. Komura, Y. Sugi
  • Journal Title: Catal. Lett. 123 Pages: 259-263
  • Peer Reviewed
• [Journal Article] Remarkable Improvement of Catalytic Performance in Dimethyl Ether to Olefin (DTO)Reaction over CeO_2 -modified Calcium-containing MFI Type Zeolite (2008)
  • Author(s): A. Iida, R. Nakamura, K. Komura, Y. Sugi
  • Journal Title: Chem. Lett. 37 Pages: 494-495
  • Peer Reviewed
• [Journal Article] New Synthesis Route to Nano-sized β-Zeolite in the Presence of a Cationic Surfactant Containing Siloxane Moiety (2008)
  • Author(s): C. Venkatesan, K. Komura, Y. Sugi
  • Journal Title: Chem. Lett. 37 Pages: 668-669
  • Peer Reviewed
• [Journal Article] The Alkylation of Naphthalene over One-dimensional Fourteen-membered Ring Zeolites. The Influence of Zeolite structure and Alkylating Agents on the Selectivity for Dialkylnaphthalenes (2008)
  • Author(s): Y. Sugi, H. Maekawa, H. Naiki, K. Komura, Y. Kubota
  • Journal Title: Bull. Chem. Soc. Jpn. 81 Pages: 1166-1174
  • Peer Reviewed
• [Journal Article] Synthetic Investigation on MCM-68 Zeolite with MSE Topology and its Application for Shape-Selective Alkylation of Biphenyl (2008)
  • Author(s): T. Shibata, S. Suzuki, H . Kawagoe, K. Komura, Y. Kubota, Y. Sgsi, J. -H. Kim, G. Seo
  • Journal Title: Micropor. Mesopor. Mater. 116 Pages: 216-226
  • Peer Reviewed
• [Journal Article] Multi-Valent Metal Salts as Versatile Catalyst for the Amidation of Long-chain Aliphatic Acid with Aliphatic Amine (2008)
  • Author(s): Y Terada, N. Ieda, K. Komura, Y. Sugi
  • Journal Title: Synthesis 2008 Pages: 2318-2320
  • Peer Reviewed
• [Journal Article] FeCl_3・6H_2O as a Versatile Catalyst for the Esterification of Steroid Alcohols with Fatty Acids (2008)
  • Author(s): K. Komura, A. Ozaki, N. Ieda, Y. Sugi
  • Journal Title: Synthesis 2008 Pages: 3407-3410
  • Peer Reviewed
• [Journal Article] Quinoline-Carboimine Derived Palladium Complexes Immobillized on Ordered Mesoporous Silica as Catalysts for Sonogashira Coupling Reactions (2008)
  • Author(s): H. Nakamura, K. Komura, Y. Sugi
  • Journal Title: J. Mol. Catal. A : Chemical 293 Pages: 72-78
  • Peer Reviewed
• [Journal Article] Product Selectivity and Catalytic Deactivation of MOR Zeolites with Different Acid Site Densities in Methanll-to-Olefin Reaction (2008)
  • Author(s): J. W. Park, S. J. Kim, M. E. Seo, S. Y. Kim, Y. Sugi, G. Seo
  • Journal Title: Appl. Catal. A : General 349 Pages: 76-85
  • Peer Reviewed
• [Journal Article] Multi-Valent Metal Salt Hydrates as Catalysts for the Esterification of Fatty Acids and Alcohols (2008)
  • Author(s): N. Ieda, K. Mant, R. Nakamur a, Y. Miya, K. Komura, Y. Sugi
  • Journal Title: Ind. Eng. Chem. Res. 47 Pages: 8631-8638
  • Peer Reviewed
• [Journal Article] Synthesis of Nano-sized β-Zeolites by Dry Gel Conversion (DGC) Method with the Use of Sodium Hydroxide (2008)
  • Author(s): A. Sakthivel, A. Iida, K. Komura, Y. Sugi
  • Journal Title: Nanoporous Materials Pages: 79-88
  • Peer Reviewed
• [Journal Article] Quinoline-Carboimine Palladium Complex Immobilized on MCM-41 as a Versatile Catalyst for Sonogashira Corss Coupling Reaction (2008)
  • Author(s): H. Nakamura, K. Komura, Y. Sugi
  • Journal Title: Nanoporous Materials Pages: 561-570
  • Peer Reviewed
• [Journal Article] A New Synthesis Route to Nano-sized β-Zeolite with Organic Silane Containing Surfactant (2008)
  • Author(s): C. Venkatesan, K. Aoyama, K. Komura, Y. Sugi
  • Journal Title: Stud. Surf. Sci. Catal. 174A Pages: 225-228
  • Peer Reviewed
• [Presentation] Heterogeneous Aza-Henry reaction of aldimine with nitromethane catalyzed by zeolite catalysts for the synthesis of beta-nitroamine compounds. (2009)
  • Author(s): K. Komura, Y. Taninaka, Y. Sugi
  • Organizer: National Catalysis Symposium, Catalysis Society of India
  • Place of Presentation: Pune, India
  • Year and Date: 2009-01-18
• [Presentation] 結晶性層状ケイ酸塩(K-LDS)の合成と特長、機能化に向けて (2008)
  • Author(s): 小村賢一, 上中麻奈未, 池田卓史, 杉義弘
  • Organizer: ゼオライト研究発表会
  • Place of Presentation: 東京
  • Year and Date: 2008-11-27
• [Presentation] ゼオライトの形状選択性-ビフェニルのアルキル化を例として (2008)
  • Author(s): 杉義弘
  • Organizer: ゼオライト研究発表会
  • Place of Presentation: 東京
  • Year and Date: 2008-11-26
• [Presentation] A New Synthesis Route to Nano-sized β-Zeolite with Organic Silane Containing Surfactant (2008)
  • Author(s): C. Venkatesan, K. Aoyama, K. Komura, and Y. Sugi
  • Organizer: 4th International FEZA Conference (FEZA2008)
  • Place of Presentation: Paris, France
  • Year and Date: 2008-08-30
• [Presentation] Shape-selective isopropylation of isobutylbenzene in supercritical C0_2 over H-mordenite (2008)
  • Author(s): S. Laha, K. Komura, Y. Sugi
  • Organizer: 14th International Congress on Catalysis
  • Place of Presentation: Seoul, Korea
  • Year and Date: 2008-07-17
• [Presentation] Template free, hydrothermally treated aluminosilicate gels : Viable precursors for mesoporous and microporous aluminosilicates (2008)
  • Author(s): C. Venkatesan, K. Komura, Y. Sugi, Y. Sasaki, M. Kobayashi
  • Organizer: International Symposium on Creation and Control of Advanced Selective Catalysis, A Pre-Symposium of 14th International Congress on Catalysis (Pre-ICC14, Kvoto2008)
  • Place of Presentation: 京都
  • Year and Date: 2008-07-10
• [Presentation] Multi-valent metal salt hydrates as catalysts for the esterification of fatty acids and alcohols (2008)
  • Author(s): N. Ieda, K. Mantri, Y. Miyata, K., Y. Sugi
  • Organizer: International Symposium on Creation and Control of Advanced Selective Catalysis, A Pre-Symposium of 14th International Congress on Catalysis (Pre-ICC14, Kyoto2008)
  • Place of Presentation: 京都
  • Year and Date: 2008-07-09
• [Presentation] Quinoline-Carboimine Palladium Complex Immobilized on MCM-41 as a Versatile Catalyst for Sonogashira Corss Coupling Reaction (2008)
  • Author(s): H. Nakamura, K. Komura, Y. Sugi
  • Organizer: Nanoporous Materials, the 5th International Symposium
  • Place of Presentation: Vancouver, Canada
  • Year and Date: 2008-05-26
• [Presentation] Synthesis of Nano-sized β-Zeolites by Dry Gel Conversion (DGC) Method with the Use of Sodium Hydroxide (2008)
  • Author(s): A. Sakthivel, A. Iida, K. Komura, Y. Sugi
  • Organizer: Nanoporous Materials, the 5th International Symposium
  • Place of Presentation: Vancouver, Canada
  • Year and Date: 2008-05-25
• [Presentation] The alkylation of biphenyl over zeolites. The influences of zeolite structure and alkylating agent on the shape-selective catalysis (2008)
  • Author(s): Y. Sugi
  • Organizer: International Symposium on Zeolite Catalysis for Green Chemistry in Synthesis of chemicals and Fuels, 235th ACS National Meeting
  • Place of Presentation: New Orleans, U.S.A.
  • Year and Date: 2008-04-07
• [Book] ゼオライト, 環境対応型セラミックスの技術と応用 (2008)
  • Author(s): 小村賢一, 杉義弘
  • Total Pages: 400
  • Publisher: シーエムシー
• [Book] 天然ガス資源とその応用技術 (2008)
  • Author(s): 杉義弘, 浜田秀昭
  • Total Pages: 350
  • Publisher: シーエムシー
• [Patent(Industrial Property Rights)] カルボン酸ステロイドエステルの製造方法 (2008)
  • Inventor(s): 杉義弘小村賢一尾崎彰禎岸田徹家田昇
  • Industrial Property Rights Holder: 日生化学工業所
  • Industrial Property Number: 特願2008-212072
  • Filing Date: 2008-08-20
• [Patent(Industrial Property Rights)] 新規メソポーラスアルミノシリゲートの製造法 (2008)
  • Inventor(s): 杉義弘, C. Ventakesa小村賢一
  • Industrial Property Rights Holder: 触媒化成, 杉義弘
  • Industrial Property Number: 特願2008-335392
  • Acquisition Date: 2008-12-27