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Parial Oxidation of Aromatics with Activated-Oxygen Cell Reactions

Research Project

Project/Area Number 04453078
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 工業物理化学・複合材料
Research InstitutionTokyo Institute of Technology

Principal Investigator

OTSUKA Kiyoshi  Tokyo Institute of Technology Chem. Eng Associate Professor, 工学部, 助教授 (60016532)

Co-Investigator(Kenkyū-buntansha) YAMANAKA Ichiro  Tokyo Institute of Technology Chem. Eng Associate Professor, 工学部, 助手 (90240051)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1993: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1992: ¥3,500,000 (Direct Cost: ¥3,500,000)
KeywordsHudroxylation of benzene. / One step sunthesis of phenol. / Fuel cell. / Partial of toluene. / Selective synthesis of cresol. / Selective synthesis of benzaldehyde. / Carbon electrode. / Hydroxy radical. / 酸素酸化 / ベンゼル水酸化 / フェノール段合成
Research Abstract

One step synthesis of phenol from benzene with reductivated O2 over the cathode was a success by applying an H2 cell reaction system. Cathodes of some carbon materials activated woth HNO3 aq. at refluxing were active for the hydroxylation of benzene. The order of the cathodes for the yield of products was carbon whisker a10 carbon black >> active carbon > graphite.The co-addition of Pd black and Fe2O3 and the addition of CuSO 4 to carbon whisker enhanced the catalytic acticity of the cathode for the hydroxylation of benzene. Especially, the maximum yield of phenol was obtained during generating electricity at 0.3 V for the cathode of carbon whiskeradded CuSO4. This result demonstrates that the possibility of phenol and electroricity. The oxidation of toluene occurredwith our reaction system, producing o-, m-, p-cresols and benzaldehyde, benzyl alcohol. The selectiviy to cresols was high for the cathode of carbom black and active carbon, that to benzaldehyde and benzyl alcohol was high for the cathode of carbon whisker and graphite. The selectivities of the products can be controlled by changing the oncentration of the electrolyte solutions of H3PO4. Cresols were selectively produced (90%) at low concentration of H3PO4, and benzaldehyde was selectively produced (95%) at high concentration. The synergistic effect of active carbon and carbon whisker for the oxidation of toluene was observed. The catalytic activity for the cathode of the mixture of active carbon andcarbon whisker (1 : 1) was 6 tumes of that for active carbon alone and twice of that for carbon whisker alone. These observations could be explained by a Fenton-type chemistry assuming HO・ as an active oxugen.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (33 results)

All Other

All Publications (33 results)

  • [Publications] Kiyoshi Otsuka: "Regioselective Oxidation of n-Hexane and Aromatics in the presence of cyclodextrins during H_2-O_2 Fuel Cell Reactions" Electrochimica Acta. 37. 1135-1141 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Synthesis of Cresols by Appling H_2-O_2 Fuel Cell Reaction" Electrochimica Acta. 37. 2549-2552 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Toluene to Benzaldehyde and Benzyl Alcohol by Appling Fuel Cell System" Chemistry Letters. 773-776 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Direct Synthesis of Phenol from Benzene during O_2-H_2 Fuel Cell Reactions" Jounal of Electrochemical Society. 139. 2381-2386 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 大塚 潔: "H_2-O_2電池反応を応用した芳香族の水酸化" 化学工学. 56. 834-836 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Benzene over the Carbon Whisker Cathode Added with Iron(III)Oxide and Pd Black during O_2-H_2 Fuel Cell Reactions" 183rd Meeting of The Electrochemical Society. 1754 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Toluene by Reductively Activated Oxygen on the Cathodes of Various Carbon Materials" 183rd Meeting of The Electrochemical Society. 1636 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 大塚 潔: "ケミカルズ/電力コジェネレーション法によるフェノールの一段合成" 触媒. 35. 422-425 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka: "Partial Oxidation of Alkanes and Aromatics with Activated Oxygen over an SmCl_3-Embedded Graphite Cathode" Journal of Alloys and Compounds. 193. 56-58 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka: "Partial oxidation of Cyclohexane with Reductively Activated Dioxygen on SmCl_3 supported on Graphite during H_2-O_2 Fuel Cell Reactions" Journal of Chemical Society,Faraday Transactions. 89. 1791-1797 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka: "Investigation of the Nature of the Active Oxygen Intermediate at Graphite-supported SmCl_3 and FeCl_3 working as a Cathode for the Partial oxidation of Alkanes and Aromatics" Journal of Chemical Society,Faraday Transactions. (in press). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka and Kenji Furuya: ""Regioselective Oxidation of n-Hexane and Aromatics in the presence of cyclodextrins during H2-O2 Fuel Cell Reactions"" Electrochimica Acta. 37, [6]. 1135-1141 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, and Kiyotaka Ishizuka, and Ichiro Yamanaka: ""Synthesis of Cresols by Appling H2-O2 Fuel Cell Reaction"" Electrochimica Acta. 37, [13]. 2549-2552 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, and Kiyotaka Ishizuka, and Ichiro Yamanaka: ""Partial Oxidation of Toluene to Benzaldehyde and Benzyl Alchol by Appling Fuel Cell SyStem"" Chemistry Letters.773-776 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, Mitsuhiro KUnieda, and Hideaki Yamagata: ""Direct Synthesis of Phenol from Benzene During O2-H2 Fuel Cell Reactions"" Jounal of Electro ch emical. 139, [9]. 2381-2386 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: ""The Hydoroxylation of Aromatics Appling H2-O2 Fuel Cell Reactions"" Kagakukougaku. 56. 834-536 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka and Kiyoshi Otsuka: ""Partial Oxidation of Alkanes and Aromatics with Activated Oxygen over an SmCl3 Embedded Graphite Cathode"" Journal of Alloys and Compounds. 193. 56-58 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, Mithhiro Kunieda, and Ichiro Yamanaka: ""Partial Oxidation of Benzene over the Carbon Whisker Cathode Added with Iron (III) Oxide and Pd Black during O2-H2 Fuel Cell Reactions"" 183rd Meeting of The Electrochemical Society, 1754. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, Ichiro Yamanaka, and Kiyotaka Ishizuka: ""Partial Oxidation of Toluene by Reductively Activated Oxugen on the Cathodes of Various Carbon Materials"" 183rd Meeting of The Electrochemical Society, 1636. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka, Ichiro Yamanaka, and Mitsuhiro Kunieda: ""One-step Synthesis of Phenol from benzene by using a Cegeneration System for Chemicals and Electricity"" Shokudai. 35, [6]. 422-425 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka and Kiyoshi Otsuka: ""Partial oxidation of Cyclohexane with Reductively Activated Dioxygen on SmCl3 supported on Graphite during H2-O2 Fuel Cell Reactions"" Journal of Chemical Society, Faraday Transactions. 89[11]. 1790-1797 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Ichiro Yamanaka and Kiyoshi Otsuka: ""Investigation of the Nature of the Active Oxygen Intermediate at Graphite-supported SmCl3 and FeCl3 working as a Cathode for the Partial oxidation of Alkanes and Aromatics"" Journal of Chemical Society, Faraday Transactions. (in press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Benzene over the Carbon Whisker Cathode Added with Iron(III)Oxide and Pd Black during O_2-H_2 Fuel Cell Reactions" 183rd Meeting of The Electrochemical Society. 1754 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Toluene by Reductively Activated Oxygen on the Cathodes of Various Carbon Materials" 183rd Meeting of The Electrochemical Society. 1636 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 大塚 潔: "ケミカルズ/電力コジェネレーション法によるフェノールの一段合成" 触媒. 35. 422-425 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Ichiro Yamanaka: "Partial Oxidation of Alkanes and Aromatics with Activated Oxygen over an SmCl_3-Embedded Graphite Cathode" Journal of Alloys and Compounds. 193. 56-58 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Ichiro Yamanaka: "Partial oxidation of Cyclohexane with Reductively Activated Dioxygen on SmCl_3 supported on Graphite during H_2-O_2 Fuel Cell Reactions" Journal of Chemical Society,Faraday Transactions. 89. 1791-1797 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Ichiro Yamanaka: "Investigation of the Nature of the Active Oxygen Intermediate at Graphite-supported SmCl_3 and FeCl_3 working as a Cathode for the Partial oxidation of Alkanes and Aromatics" Journal of Chemical Society,Faraday Transactions. (in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kiyoshi Otsuka: "Regioselective Oxidation of n-Hexane and Aromatics in the Presence of Cyclodextrins during H2-02 Fuel Cell Reactions" Electrochimica Acta. 37. 1135-1141 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Kiyoshi Ostuka: "Synthesis of Cresols by Appling H2-02 Fuel Cell Reaction" Electrochimica Acta. 37. 2549-2552 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Kiyoshi Otsuka: "Partial Oxidation of Toluene to Benzaldehyde and Benzy Alcohol by applying Fuel Cell System" Chemistry Letter. 773-776 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Kiyoshi Otsuka: "Direct Synthesis of Phenol from Benzene during 02-H2 Fuel Cell Reactions" Journal of Electrochemical Society. 139. 2381-2386 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 大塚 潔: "H2-02電池反応を応用した芳香族の水酸化" 化学工学. 56. 834-836 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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