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Oxidation of Hydrocarbons Catalyzed by mu-Oxopolynuclear Mixed Metal Complexes

Research Project

Project/Area Number 02650586
Research Category

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

Allocation TypeSingle-year Grants
Research Field 工業物理化学・複合材料
Research InstitutionKyoto Prefectural University

Principal Investigator

KANAI Hiroyoshi  Kyoto Prefectural University, Faculty of Living Science, Professor, 生活科学部, 教授 (40026050)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1991: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1990: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsPolynuclear metal complexes / oxidation / mixed valence / mixed metal complexes / mu-oxo / oxidative dehydrogenation / carbon monooxide oxidation / オキソ / 酸素酸化反応 / μーオキソ
Research Abstract

(1) The oxidation of styrene has been carried out in O_2 atmosphere with mu-oxotrinuclear ironcarboxylates, [Fe_3O(O_2CR)_6(H_2O)_3]^+. Small differences were found for oxidation rates among complexes which were dissolved in styrene. Relatively high epoxide selectivity was obtained for complexes with carboxylates, their acid strength(pKa) of nearly 4. Benzoate ligands whose Hammett values are from small negative figures to zero gave maximum epoxide selectivity(28%). (2) In the oxidation with mu-oxotrinuclear mixed valence metal carboxylates Fe_2^<III>Fe^<II> and Co_2^<III>Co^<II> are superior in the oxidation rates and epoxide selectivity to their homovalence complexes. Its homologue, V_2^<IV>V^<III> is also effective. However, Mn_2^<III>Mn^<II> has none of effectiveness. Among mixed metal (Fe_2^<III>M^<II>, M = Mn, Co, Ni, Zn, Mg) acetate complexes zinc exerted highest epoxide selectivity(35% at 85゚C). No activity was observed for Fe_2^<III>Mn^<II> complex. Almost the same epoxide sel … More ectivity with that for Fe_2III^<Zn>II^< was found for Cr_2>IIIFe^<II> complex. (3) The oxidation was slow at room temperature and requires higher than 70゚C. The oxidation rate increases with the increase of temperature and reaches maximum at 95゚C. Differences of activity and epoxide selectivity are observed among complexes at low temperatures but were leveled off above 95゚C. Highest epoxide selectivity was found at 85-95゚C. The decrease of oxygen pressure decreased oxidation rate, but increased epoxide selectivity. Higher than 50% of epoxide was obtained at less than 13 kPa of O_2 pressure. (4) Clustered metal oxide catalysts(Fe loading 7.8 wt%) with 3 metals were prepared by impregnating Fe_2^<III>M^<II>O(OAc)_6(H_2O)_3 (M = Fe, Mg, Zn, Mn, Co, Ni) on SiO_2 followed by calcination. Dehydrogenation of 1-butane to butadiene at 573K were carried out with those catalysts; higher activities than that for M = Fe were obtained for M = Mn and Zn, almost the same for M = Co and Ni, and no activity was observed for M = Mg. Selectivities to butadiene are 71%(Zn), 68%(Fe), 67%(Co) and 53%(Ni). Less

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] H.Kanai: "Oxidation of Styrene Catalyzed by μ-Oxotrinuclear Mixed Valence and Mixed Metal Carboxylate Complexes" J.Catalysis. 138. 611-616 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Nakayama: "Synthetic Fluorotetrasilisic Mica as a Support for Stereoselective Catalysts" J.Materials Science.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T.Nakayama: "Catalysis of Transition Metal Intercalated Layered Silicates" Clay Science.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 金井 宏俶: "μ-オキソ三核鉄カルボキシラート錯体によるスチレンの酸素酸化によるベンズアルデヒド合成" 日化.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Kanai: "Oxidation of Styrene Catalyzed by mu-Oxotrinuclear Mixed Valence and Mixed Metal Carboxylates Complexes" J. Catalysis. 138. 611-616 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Nakayama: "Synthetic Fluorotetrasilisic Mica as a Support for Stereoselective Catalysts" J. Materials Science.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Nakayama: "Catalysis of Transition Metal Intercalated Layered Silicates" Clay Science.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Kanai: "Synthesis of Benzaldehyde in the Oxidation of Styrene Catalyzed by mu-Oxotrinuclear Iron Carboxylates" Nippon Kagaku Kaishi.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H.Kanai: "Oxidation of Styrene Catalyzed by μーOxotrinuclear Mixed Valence and Mixed Metal Carboxylate Complexes" J.Catalysis.

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Nakayama: "Catalysis by Transition Metal Exchanged Intercalation CompoundsーWater Gas Shift Reaction and Hydrogenation of Conjugated Dienes" J.Japan Petroleum Institute.

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Kanai: "Oxidation of Olefins Catalyzed by μーOxotrinuclear Mixed Metal Carboxylates and Their Application to Preparation of Mixed Metal Oxide Catalysts" The Proceedings of 7th Intern.Symposium on Relation between Humogeneous and Heterogeneous Catalysis,in press.

    • Related Report
      1991 Annual Research Report
  • [Publications] 金井 宏俶: "μーオキソ三核鉄カルボキシラ-ト錯体用いたステレンの酸素酸化によるベンズアルデヒドの合成" 日化.

    • Related Report
      1991 Annual Research Report
  • [Publications] 金井 宏俶: "Oxydation of Styrenes Catalyzed by μーOxotrinuclear Iron Carboxylate Complexes" J.Catalysis.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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