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Partial oxidation of cyclohexane into cyclohexanone and cyclohexanol (KA-oil) is an industrially significant reaction for producing precursors for the synthesis of ε-caprolactam and adipic acid, which are the building blocks of nylon. However, to date, the cyclohexane conversion ratio has usually been limited to less than 6% to prevent further oxidation of the cyclohexanol and cyclohexanone targets. In this study, we report that Pt/CeO2–ZrO2–SnO2/SiO2, in which CeO2–ZrO2–SnO2 provide reactive oxygen molecules from inside the bulk, can act as efficient catalysts. Optimization of the catalyst composition and reaction conditions provided a cyclohexane conversion ratio of 24.1% and a total selectivity for cyclohexanol and cyclohexanone of 83.4% at 130 ℃ in 0.5 MPa (4.9 atm) air for 7 h over a 5wt%Pt/16wt%Ce0.68Zr0.17Sn0.15O2.0/SiO2 catalyst. This catalyst has significant advantages over conventional catalysts because the reaction proceeds at a lower pressure, and there is no need for toxic radical initiators or free-radical scavengers.


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Selective liquid phase oxidation of cyclohexane over Pt/CeO2–ZrO2–SnO2/SiO2 catalysts with molecular oxygen

Show Author's information Nobuhito IMANAKA( )Toshiyuki MASUIKazuya JYOKO
Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

Abstract

Partial oxidation of cyclohexane into cyclohexanone and cyclohexanol (KA-oil) is an industrially significant reaction for producing precursors for the synthesis of ε-caprolactam and adipic acid, which are the building blocks of nylon. However, to date, the cyclohexane conversion ratio has usually been limited to less than 6% to prevent further oxidation of the cyclohexanol and cyclohexanone targets. In this study, we report that Pt/CeO2–ZrO2–SnO2/SiO2, in which CeO2–ZrO2–SnO2 provide reactive oxygen molecules from inside the bulk, can act as efficient catalysts. Optimization of the catalyst composition and reaction conditions provided a cyclohexane conversion ratio of 24.1% and a total selectivity for cyclohexanol and cyclohexanone of 83.4% at 130 ℃ in 0.5 MPa (4.9 atm) air for 7 h over a 5wt%Pt/16wt%Ce0.68Zr0.17Sn0.15O2.0/SiO2 catalyst. This catalyst has significant advantages over conventional catalysts because the reaction proceeds at a lower pressure, and there is no need for toxic radical initiators or free-radical scavengers.

Keywords:

composite materials, oxidation, cyclohexane, KA-oil, catalyst
Received: 07 November 2014 Revised: 09 December 2014 Accepted: 11 December 2014 Published: 30 May 2015 Issue date: June 2015
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Publication history
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Publication history

Received: 07 November 2014
Revised: 09 December 2014
Accepted: 11 December 2014
Published: 30 May 2015
Issue date: June 2015

Copyright

© The author(s) 2015

Acknowledgements

The authors deeply appreciate Professor Dr. S. Minakata for providing suggestions. We also thank Dr. T. Sakata and Professor Dr. H. Yasuda for technical assistance with the TEM measurements.

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