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Development of Catalysts for Selective Phenol Synthesis by Oxidation of Benzene in Gas Phase

Research Project

Project/Area Number 18560740
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Catalyst/Resource chemical process
Research InstitutionKobe University

Principal Investigator

KUMAGAI Norihisa (2007)  Kobe University, Graduate School of Engineering Department fo Chemical Science and Engineering, Technician (60437457)

鶴谷 滋 (2006)  神戸大学, 工学部, 教授 (00031120)

Co-Investigator(Kenkyū-buntansha) NISHIYAMA Satoru  Kobe University, Graduate School of Engineering Department fo Chemical Science and Engineering, Professor (00156126)
ICHIHASH Yuichi  Kobe University, Graduate School of Engineering Department fo Chemical Science and Engineering, Assistant Professor (20362759)
熊谷 宜久  神戸大学, 工学部, 技術職員 (60437457)
Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,740,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥240,000)
Fiscal Year 2007: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2006: ¥2,700,000 (Direct Cost: ¥2,700,000)
KeywordsPhenol / Benzene / Zeolite / Cupper / Difficult oxidation reaction / Coordination / Redox propert / Ti addition / 銅触媒 / 酸素 / 銅担持ZSM-5ゼオライト / カリウム / CO_2 / CO
Research Abstract

Direct phenol synthesis from benzene and molecular oxygen was investigated on Cu^<2+> ion-incorporated in ZSM-5 zeolite in gas phase. The calcinations at high temperatures improved the formation of phenol from benzene. Electron spin resonance spectra indicated that two type of Cu^<2+> ions were observed in HZSM-5 zeolites, one Cu^<2+> was bonded by oxygen with square pyramidal coordination, the other Cu^<2+> was bonded by oxygen with square planar coordination. The ratio between the pyramidal to the planar was changed by the calcinations temperature. The catalyst with the highest pyramidal Cu^<2+> indicated the highest yield of phenol. These results clearly indicate that the square pyramidal Cu^<2+> ions in HZSM-5 are active sites for direct oxidation of benzene in gas phase. Reduction behavior of Cu^<2+> ions in HZSM-5 was also studied by CO adsorption on the catalysts after evacuation at high temperatures. Carbon monoxide molecules are adsorbed not on Cu^<2+> and Cu^0 but on Cu. The … More catalyst with the highest pyramidal Cu^<2+> indicated that Cu^<2+> was readily reduced to Cu^+ by the evacuation. These results indicate that the pyramidal Cu^<2+> ions have high redox capacity. Benzene oxidation to phenol would proceed as follows;
1) Cu^<2+> is reduced to Cu^+ by a reducing agent (benzene, CO, etc.)
2) Cu^+ activates an oxygen molecule and produces specific oxygen species.
3) The specific oxygen species reacts with benzene and phenol is selectively formed. So, one of the important steps in the catalytic cycle of the oxidation is considered to be the reduction of Cu^<2+>. These considerations suggest that the square pyramidal Cu^<2+> sites have high redox capacity and form the specific oxygen species which produces phenol directly.
To control the redox property of the catalysts, addition of Ti and alkaline metals was investigated. The addition of Ti to Cu/HZSM-5 catalysts improved the activity of phenol formation. Electron spin resonance spectra and CO adsorption experiments indicated that the presence of Ti or alkaline metal neighboring Cu^<2+> ions would promote redox property. Less

Report

(3 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • Research Products

    (14 results)

All 2008 2007 2006 2005 Other

All Journal Article (11 results) (of which Peer Reviewed: 5 results) Presentation (3 results)

  • [Journal Article] 酸化チタン光触媒を用いたメタンの光水蒸気改質反応による水素製造法2008

    • Author(s)
      市橋 祐一
    • Journal Title

      燃料電池 7

      Pages: 82-87

    • NAID

      40015853213

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] WO_3-TiO_2複合酸化物を光触媒とした可視光照射下でのシクロヘキサンの光酸化反応2007

    • Author(s)
      市橋 祐一
    • Journal Title

      触媒 49

      Pages: 385-387

    • NAID

      10019844349

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Zinc Powder as an Effective Reducing Reagent during Liquid-Phase Oxidation of Benzene to Phenol Using Molecular Oxygen over V-Substituted Heteropoly Acid Catalysts2006

    • Author(s)
      Sumimuto, C. Tanaka, S. Yamaguchi, Y. Ichihashi, S. Nishiyama, S. Tsuruya
    • Journal Title

      Industrial & Engineering Chemistry Research 45

      Pages: 7444-7450

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Zinc Powder as an Effective Reducing Reagent during Liquid-Phase Oxidation of Benzene to Phenol Using Molecular Oxygen over V-Substituted Heteropoly Acid Catalysts2006

    • Author(s)
      S.Sumimoto
    • Journal Title

      Industrial & Engineering Chemical Research 第45巻

      Pages: 7444-7450

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Promoted Partial Oxidation Activity of Alkali Metal Added-Co Catalysts Supported on NaY and NaUSY Zeolites in the Gas-Phase Catalytic Oxidation of Benzyl Alcohol2006

    • Author(s)
      D.Nakashima
    • Journal Title

      Journal of Molecular Catalysis A : Chemical 第259巻

      Pages: 108-115

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Promoting Effect and Role of Alkaline Earth Metal Added to Supported Ag Catalysts in the Gas-Phase Catalytic Oxidation of Benzyl Alcohol2006

    • Author(s)
      Y.Sawayama
    • Journal Title

      Industrial & Engineering Chemical Research 第45巻

      Pages: 8837-8845

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Gas-Phase Catalytic Oxidation of Benzene to Phenol over Cu-Impregnated HZSM-5 Catalysts2005

    • Author(s)
      Y. Shibata
    • Journal Title

      Industrial & Engineering Chemistry Research 44

      Pages: 8765-8772

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Gas-Phase Catalytic Oxidation of Benzene to Phenol over Cu-Impregnated HZSM-5 Catalysts2005

    • Author(s)
      Y. Shibata, R. Hamada, T. Ueda, Y. Ichihashi, S. Nishiyama, S. Tsuruya
    • Journal Title

      Industrial & Engineering Chemistry Research 44

      Pages: 8765-8772

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Liquid-Phase Oxidation of Benzene to Phenol by Molecular Oxygen over La Catalysts

    • Author(s)
      Y. Ichihashi
    • Journal Title

      Topics in Catalysis (in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Liquid-Phase Oxidation of Benzene to Phenol by Molecular Oxygen over La Catalysts Supported on HZSM-5

    • Author(s)
      Y. Ichihashi, T. Taniguchi, H. Amano, T. Atsumi, S. Nishiyama, S. Tsuruya
    • Journal Title

      Topics in Catalysis (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Liquid-Phase Oxidation of Benzene to Phenol by Molecular Oxygen over La Catalysts

    • Author(s)
      Y. Ichihashi
    • Journal Title

      Topics in Catalysis (in press)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] Gas-Phase Catalytic Oxidation of Benzene to Phenol over Cu/Ti/HZSM-5 Catalysts2007

    • Author(s)
      Y. Kamizaki
    • Organizer
      The 11th Korea-Japan Symposium on Catalysis
    • Place of Presentation
      Seoul, Korea
    • Year and Date
      2007-05-21
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] アルカリおよびアルカリ土類金属担持Cu/HZSM-5触媒を用いたベンゼンの気相接触酸化反応2007

    • Author(s)
      神崎 洋平
    • Organizer
      第99回触媒討論会
    • Place of Presentation
      神戸
    • Year and Date
      2007-03-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] Gas-Phase Catalytic Oxidation of Benzene to Phenol over Cu/Ti/HZSM-5 Catalysts2007

    • Author(s)
      Y. Kamizaki, N. Terai, Y. Ichihashi, S. Nishiyama, S. Tsuruya
    • Organizer
      The 11th Korea-Japan Symposium on Catalysis
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary

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Published: 2006-04-01   Modified: 2016-04-21  

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