Rate Enhancement and selectivity Control of Liquid Phase Organic Reactions by Chemical Effects of Dense Phase Carbon Dioxide

• Project/Area Number: 18360378
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Reaction engineering/Process system
• Research Institution: Hokkaido University
• Principal Investigator: ARAI Masahiko Hokkaido University, 大学院・工学研究科, 教授 (60125490)
• Co-Investigator(Kenkyū-buntansha): FUJITA Shin-ichiro 北海道大学, 大学院・工学研究科, 講師 (80156869) ; SHIMOKAWABE Masahide 北海道大学, 大学院・工学研究科, 准教授 (40125323) ; IWASA Nobuhiro 北海道大学, 大学院・工学研究科, 助教 (30223374)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥10,990,000 (Direct Cost: ¥9,700,000、Indirect Cost: ¥1,290,000); Fiscal Year 2008: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2007: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2006: ¥5,400,000 (Direct Cost: ¥5,400,000)
• Keywords: 超臨界二酸化炭素 / 特殊反応場 / 選択的水素化 / 選択性 / 圧力効果 / 反応制御 / 反応選択性

Research Abstract

液体反応物を反応物ではない二酸化炭素で加圧して反応を行うと, 二酸化炭素の圧力によって反応の速度と生成物の分布が大きく変化することを幾つかの有機合成反応で実証した。二酸化炭素が, 有機合成反応の促進剤あるいは制御剤として作用することを見出した。加圧条件では二酸化炭素は液体反応物中に溶解し, 溶解した二酸化炭素分子が反応物の反応性を変える機能を有することを赤外線の吸収を利用した方法で示した。

Research Products

• [Journal Article] Multiphase catalytic reactions in/under dense phaseCO_2 (2009)
  • Author(s): M. Arai, S. Fujita, M. Shirai
  • Journal Title: J. Supercrit. Fluids 47 Pages: 351-356
  • Peer Reviewed
• [Journal Article] A comparative study of strong metal-support interaction and catalytic behavior of Pd catalysts supported on micron-and nano-sized TiO_2 in liquid-phase selective hydrogenation of phenylacetylene (2008)
  • Author(s): P. Weerachawanasak, P. Praserthdam, M. Arai, J. Panpranot
  • Journal Title: Journal of Molecular Catalysis A : Chemical 279 Pages: 133-139
  • Peer Reviewed
• [Journal Article] Hydrogenation of phenol in scCO_2 over carbon nanofiber supported Rh catalyst (2008)
  • Author(s): H. Wang, F. Zhao, S. Fujita, M. Arai
  • Journal Title: Catalysis Communications 9 Pages: 362-368
  • Peer Reviewed
• [Journal Article] An in situ high pressure FTIR study on molecular interactions of ketones, esters, and amides with dense phase carbon dioxide (2008)
  • Author(s): Y. Akiyama, S. Fujita, H. Senboku, C. M. Rayner, S. A. Brough, M. Arai
  • Journal Title: Journal of Supercritical Fluids 46 Pages: 197-205
  • Peer Reviewed
• [Journal Article] Impact of carbon dioxide pressurization on liquid phase organic reactions : A case study on Heck and Diels-Alder reactions (2008)
  • Author(s): S. Fujita, T. Tanaka, Y. Akiyama, K. Asai, J. Hao, F. Zhao, M. Arai
  • Journal Title: Advanced Synthesis & Catalysis 350 Pages: 1615-1625
  • Peer Reviewed
• [Journal Article] Influence of compressed carbon dioxide on hydrogenation reactions in cyclohexane with a Pd / C catalyst (2008)
  • Author(s): J. Hao, C. Xi, H. Cheng, R. Liu, S. Cai, M. Arai, F. Zhao
  • Journal Title: Industrial & Engineering Chegistry Resarch 47 Pages: 6796-6800
  • Peer Reviewed
• [Journal Article] Selective hydrogenation of unsaturated aldehydes in poly (ethylene glycol) / supercritical carbon dioxide biphasic system (2008)
  • Author(s): R Liu, H. Cheng Q. Wang, C. Wu, J. Ming, C. Xi, Y. Yu, S. Cai F. Zhao. M. Arai
  • Journal Title: Green Chemistry 10 Pages: 1082-1086
  • Peer Reviewed
• [Journal Article] Impact of palladium silicide formation on the catalytic properties of Pd/SiO_2 catalysts in liquid phase semihydrogenation of phenylacetylene (2007)
  • Author(s): J. Panpranot, K. Phandinthong, T. Sirikajorn, M. Arai, P. Praserthdam
  • Journal Title: J. Mol. Catal. A Chem. 261 Pages: 29-35
  • Peer Reviewed
• [Journal Article] Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide (2007)
  • Author(s): S. Fujita
  • Journal Title: J. Mol. Catal. A Chem. 268 Pages: 244-250
  • NAID: 120000966751
  • Peer Reviewed
• [Journal Article] Hydroformylation of cyclohexene with carbon dioxide and hydrogenusing ruthenium carbonyl catalyst: Influence of pressures of gaseous components (2007)
  • Author(s): S. Fujita
  • Journal Title: Int. J. Mol. Sci 8 Pages: 749-759
  • Peer Reviewed
• [Journal Article] Hydrogenation of phenol in scCO_2 over carbon nanofiber supported Rh catalyst (2007)
  • Author(s): H. Wang
  • Journal Title: Catal. Commun. 9 Pages: 362-368
  • Peer Reviewed
• [Journal Article] Selective hydrogenation of citral with transition metal complexes in supercritical carbon dioxide (2007)
  • Author(s): R.Liu
  • Journal Title: Applied Catalysis A : General 316・2 Pages: 127-133
• [Journal Article] Developments and applications of supported liquid phase catalysts (2006)
  • Author(s): F. Zhao, S. Fujita, M. Arai
  • Journal Title: Curr. Org. Chem. 10 Pages: 1681-1695
  • Peer Reviewed
• [Journal Article] Recyclability of water-soluble ruthenium-phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide (2006)
  • Author(s): S.Fujita
  • Journal Title: Journal of Molecular Catalysis A : Chemical 249・1-2 Pages: 223-229
  • NAID: 120000955136
• [Journal Article] A comparative study of liquid phase hydrogenation on Pd/SiO_2 in organic solvents and pressurized carbon dioxide : Activity change and metal leaching/sintering (2006)
  • Author(s): J.Panpranot
  • Journal Title: Journal of Molecular Catalysis A : Chemical 253・1-2 Pages: 20-24
• [Presentation] Green Synthesis of Aromatic Amines by Selective Hydrogenation of Nitroaromatics in Dense Phase CO_2 (2009)
  • Author(s): X. Meng, F. Zhao, S. Fujita, M. Arai
  • Organizer: International Symposium for Environmental Innovation Driven by Chemistry and Catalytic Science
  • Place of Presentation: Sapporo, Hokkaido Univ.
  • Year and Date: 2009-03-18
• [Presentation] Significance of Molecular Interactions for Selective Hydrogenation of Aromatic Nitro Compounds in Dense Phase CO_2 (2008)
  • Author(s): X. Meng, F. Zhao, S. Fujita, M. Arai
  • Organizer: The 2nd GCOE International Symposium
  • Place of Presentation: Sapporo, Hokkaido Univ.
  • Year and Date: 2008-12-18
• [Presentation] Significance of Molecular Interactions for Selective Hydrogenation of Aromatic Nitro Compounds in Dense Phase CO_2 (2008)
  • Author(s): Xiangchun Meng, Fengyu Zhao, Shin-ichiro Fujita, Masahiko Arai
  • Organizer: 2nd GCOE International Symposium
  • Place of Presentation: 北海道大学、札幌
  • Year and Date: 2008-12-18
• [Presentation] 高密度二酸化炭素とカルボニル化合物の分子間 相互作用 (2008)
  • Author(s): 秋山嘉成, 藤田進一郎, 荒井正彦
  • Organizer: 化学工学会第40回秋季大会
  • Place of Presentation: 仙台・東北大学
  • Year and Date: 2008-09-25
• [Presentation] 担時Rh触媒による超臨界二酸化炭素中でのフェノールの水素化 (2008)
  • Author(s): 山田卓也, 藤田進一郎, 荒井正彦
  • Organizer: 化学工学会第40回秋季大会
  • Place of Presentation: 仙台・東北大学
  • Year and Date: 2008-09-25
• [Presentation] 高密度二酸化炭素とカルボニル化合物の分子間相互作用 (2008)
  • Author(s): 秋山嘉成, 藤田進一郎, 荒井正彦
  • Organizer: 化学工学会第40回秋季大会
  • Place of Presentation: 東北大学、仙台
  • Year and Date: 2008-09-25
• [Presentation] 担時Rh触媒による超臨界二酸化炭素中でのフェノールの水素化 (2008)
  • Author(s): 山田卓也, 藤田進一郎, 荒井正彦
  • Organizer: 化学工学会第40回秋季大会
  • Place of Presentation: 東北大学、仙台
  • Year and Date: 2008-09-25
• [Presentation] 担持Rh触媒を用いたフェノール水素化に対する加圧二酸化炭素の影響 (2008)
  • Author(s): 山田卓也, 藤田進一郎, 荒井正彦
  • Organizer: 第17回化学工学・粉体工学研究発表会
  • Place of Presentation: 函館・市産学官交流プラザ
  • Year and Date: 2008-01-25
• [Presentation] Heck反応に対する加圧二酸化炭素の効果 (2007)
  • Author(s): 田中朋子, 藤田進一郎, 秋山嘉成, 荒井正彦
  • Organizer: 化学工学会第39回秋季大会
  • Place of Presentation: 札幌・北海道大学
  • Year and Date: 2007-09-14
• [Presentation] イオン性液体を用いた二酸化炭素とアミノアルコールからの環状ウレタン合成 (2007)
  • Author(s): 藤田進一郎, 金丸嘉志, 荒井正彦
  • Organizer: 第99回触媒討論会
  • Place of Presentation: 神戸・神戸大学
  • Year and Date: 2007-03-28
• [Presentation] 超臨界二酸化炭素中でのアルデヒドの水素化 (2007)
  • Author(s): 長谷川雅士, 藤田進一郎, 荒井正彦
  • Organizer: 第16回化学工学・粉体工学研究発表会
  • Place of Presentation: 札幌・北海道大学
  • Year and Date: 2007-01-26
• [Presentation] Multiphase Catalysis in Supercritical Carbon Dioxide : Hydroformylation of 1-Hexene Using Polystyrene Supported Rhodium Catalyst (2006)
  • Author(s): S. Fujita, S. Akihara, S. Fujisawa, M. Arai
  • Organizer: 8th International Symposium on Supercritical Fluids, Kyoto
  • Place of Presentation: Kyoto International Conference Hall
  • Year and Date: 2006-11-06
• [Presentation] 合成スメクタイトによるプロピレンオキシドからの炭酸ジメチル一段合成 (2006)
  • Author(s): 藤田進一郎, 落合由里, 荒井正彦
  • Organizer: 第98回触媒討論会
  • Place of Presentation: 富山・富山国際会議場
  • Year and Date: 2006-09-26
• [Book] 超臨界流体入門(分担執筆, 化学工学会超臨界流体部会編) (2008)
  • Author(s): 荒井正彦
  • Total Pages: 237
  • Publisher: 丸善