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1990 Fiscal Year Final Research Report Summary

Development of Technique for Chemical Conversion of Natural Gas

Research Project

Project/Area Number 01470079
Research Category

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

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

Principal Investigator

MORIKAWA Akira  Tokyo Institute of Technology Professor, 工学部, 教授 (00016396)

Co-Investigator(Kenkyū-buntansha) KOMATSU Takayuki  Research Associate, 工学部, 助手 (40186797)
HATANO Masaharu  Research Associate, 工学部, 助手 (50202255)
WADA Yuji  Research Associate, 工学部, 助手 (40182985)
OTSUKA Kiyoshi  Associate Professor, 工学部, 助教授 (60016532)
Project Period (FY) 1989 – 1990
KeywordsNatural gas / Alkane / Oxidative coupling / Oxygenated / Methane / Fuel cell / Peroxide / Solid catalyst
Research Abstract

It has been found that LiNO_3-doped NiO was a catalyst effective for oxidative coupling of methane to produce ethane and ethylene. This catalyst was identified as a compound, LiNiO_2. When methane was brought into contact with LiNiO_2, methane was converted to ethylene and ethane and LiNiO_2 was changed into a mixture of Li_2O and NiO. LiNiO_2 was restored when oxygen gas was added to the system. From the Kinetic and spectroscopic studies of this catalytic system, it has been concluded that oxidative coupling of methane on LiNiO_2 proceeds through the reaction of methane with the catalyst and reoxidation of the reduced catalyst.
LiClーdoped NiO was a catalyst effective for selective formation of ethylene during oxidative coupling of methane. LiCl suppressed deep oxidation of methane and enhanced the successive oxidative dehydrogenation of ethane to ethylene.
Two effective catalysts for formation of oxygenated compounds in oxidation of alkanes with molecular oxygen have been found. One was B_2O_3-Al_2O_3, which gave acetaldehyde from ethane. The main products on this catalyst were acetaldehyde and ethylene. A mechanism including the common intermediate for the formations of the two products were proposed. Another was B_2O_3-P_2O_5, on which propane was converted to propionaldehyde, acetone, acetaldehyde, and propylene.
Oxidative coupling of methane into ethylene and ethane over LiNiO_2 was enhanced when oxygen was removed electrochemically from the catalyst through a stabilized zirconia oxygen-anion conductor. On the other hand, the same enhancement was observed over LiCl-doped NiO when oxygen was pumped to the catalyst. The mechanisms of the new catalytic systems controlled electrochemically were proposed.

  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] K.Otsuka: "Electrochemical enhancement of oxidative coupling of methane over LiClーdoped NioO using stabilized zirconia electrolyte" Catalysis Letters. 1. 423-428 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hatano: "Alkali metalーdoped transition metal oxides active for oxidative conpling of methane" Inorganica Chimica Acta. 146. 243-247 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Komatsu: "LiCl doped cobalt oxide is an active catalyst for the formation of ethylene in the oxidative coupling of methane" Catalysis Letters. 3. 317-322 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hatano: "The oxidative coupling of methane on lithium nickelate(III)" J.Chem.Soc.,Faraday Trans.1. 85. 199-206 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Otsuka: "Synthesis of C_2H_4 by partial oxidation of CH_4 over LiCl/NiO" Catalysis Today. 4. 409-419 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Otsuka: "Oxidative of methane applying a solid oxide fuel cell system" Catalysis Today. 6. 587-592 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Otsuka, K. Suga, I. Yamanaka: "Electrochemical Control for Oxidative Coupling of Methane over LiNiO_2 Using Solid Electrolytes" Chem. Lett.,. 317-318, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, K. Suga, I. Yamanaka: "Electrochemical Enhancement of Oxidative Coupling of Methane over LiClーDoped NiO Using Stabilized Zirconia Electrolyte" Catal. Lett.,. 1. 423-428

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Hatano, K. otsuka: "Alkali Metal-Doped Transition Metal Oxides Active for Oxidative Coupling of Methane" Inorg. Chim. Acta,. 146,. 243-247 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, M. Hatano, T. Komatsu: "Synthesis of C_2H_4 by Partial Oxidation of CH_4 over Transition Metal Oxides with Alkali-Chlorides." Methane Coversion, Elsevier,. 383-387, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka: "Activation and Partial Oxidation of Methane" Shokubai (Catalyst),. 30,. 248-254, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, T. Komatsu, K. Jinno, Y. Uragami, A. Morikawa: "Activation of Methane and Synthesis of Formaldehyde by Partial Oxidation" Proc. 9th Intern. Cong. Catal.,. 2,. 915-922, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, T. Komatsu, Y. Shimizu: "The Cerium Oxide Based Catalysts Active for Oxidative Coupling of Methane" Successful Design of Catalysts, Elsevier,. 43-50, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Komatsu, Y. Uragami, K. Otsuka: "Partial Oxidation of Propane over B-P Mixed Oxide Catalysts" Chem. Lett.,. 1903-1906, (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Komatsu, T. Amaya, K. Otsuka: "LiCl Doped Cobalt Oxide is an Active Catalyst for the Formation of Ethylene in the Oxidative Coupling of Methane" Catal. Lett.,. 3,. 317-322, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Hatano, K. Otsuka: "The Oxidative Coupling of Methane on Lithium Nickelate (III)" J. Chem. Soc., Faraday Trans.1, 8,. 199-206, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, Y. Murakami, Y. Wada, A. A. Said, A. Morikawa: "Oxidative Coupling of Methane, Ethane, and Propane with Sodium Peroxide at Low Temperatures" J. Catal.,. 121,. 122-130, (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Murakami, K. Otsuka, Y. Wada, A. Morikawa: "Partial Oxidation of Ethane over Boron Oxide Added Catalysts" Chem. Lett.535-538, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, M. Hatano, T. Komatsu: "Synthesis of C_2 H_4 by Partial Oxidation of CH_4 over LiCl/NiO" Catal. Today,. 4,. 409-419, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, K. Hosokawa, I. Yamanaka, Y. Wada, A. Morikawa,: "Oneーstep Oxidation of Benzene to Phenol Applying a Fuel Cell System" Electrochimica Acta,. 34,. 1485-1488, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, M. Inaida, Y. Wada, T. Komatsu, A. Morikawa: "Isotopic Studies on Oxidative Methane Coupling over Samarium Oxide" Chem. Lett.,. 1531-1534, (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Murakami, K. Otsuka, T. Wada, A. Morikawa: "The Partial Oxidation of Ethane over a B_2O_3-Al_2O_3 Catalyst" Bull. Chem. Soc. Jpn.,. 63,. 340-346, (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Otsuka, K. Suga, I. Yamanaka: Catal. Today,. 6,. 587-592, (1990)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-08-12  

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