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1993 Fiscal Year Final Research Report Summary

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)
YAMANAKA Ichiro  Tokyo Institute of Technology Chem. Eng Associate Professor (90240051)
YAMANAKA Ichiro  Tokyo Institute of Technology Chem. Eng Associate Professor (90240051)
YAMANAKA Ichiro  Tokyo Institute of Technology Chem. Eng Associate Professor (90240051)
YAMANAKA Ichiro  Tokyo Institute of Technology Chem. Eng Associate Professor (90240051)
Project Period (FY) 1992 – 1993
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.
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.

  • Research Products

    (22 results)

All Other

All Publications (22 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 1995-03-27  

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