Journal Home > Volume 4 , Issue 2

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.


menu
Abstract
Full text
Outline
About this article

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: oxidation, composite materials, catalyst, cyclohexane, KA-oil

References(20)

[1]
Musser MT. Cyclohexanol and cyclohexanone. In Ullmann’s Encyclopedia of Industrial Chemistry, Vol. 11. Weinheim:Wiley-VCH, 2012: 49-60.
[2]
Kokotailo GT, Lawton SL, Olson DH, et al. Structure of synthetic zeolite ZSM-5. Nature 1978, 272:437-438.
[3]
Kresge CT, Leonowicz ME, Roth WJ, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 1992, 359:710-712.
[4]
Zhao R, Ji D, Lv G, et al. A highly efficient oxidation of cyclohexane over Au/ZSM-5 molecular sieve catalyst with oxygen as oxidant. Chem Commun 2004, 40:904-905.
[5]
Lü G, Zhao R, Qian G, et al. A highly efficient catalyst Au/MCM-41 for selective oxidation cyclohexane using oxygen. Catal Lett 2004, 97:115-118.
[6]
Wang C, Chen L, Qi Z. One-pot synthesis of gold nanoparticles embedded in silica for cyclohexane oxidation. Catal Sci Technol 2013, 3:1123-1128.
[7]
Liu Y, Tsunoyama H, Akita T, et al. Aerobic oxidation of cyclohexane catalyzed by size-controlled Au clusters on hydroxyapatite: Size effect in the sub-2 nm regime. ACS Catal 2011, 1:2-6.
[8]
Maksimchuk NV, Kovalenko KA, Fedin VP, et al. Cyclohexane selective oxidation over metal–organic frameworks of MIL-101 family: Superior catalytic activity and selectivity. Chem Commun 2012, 48:6812-6814.
[9]
Yang X, Yu H, Peng F, et al. Confined iron nanowires enhance the catalytic activity of carbon nanotubes in the aerobic oxidation of cyclohexane. ChemSusChem 2012, 5:1213-1217.
[10]
Imanaka N, Masui T. Advanced materials for environmental catalysts. Chem Rec 2009, 9:40-50.
[11]
Imanaka N, Masui T, Yasuda K. Environmental catalysts for complete oxidation of volatile organic compounds and methane. Chem Lett 2011, 40:780-785.
[12]
Yasuda K, Masui T, Imanaka N. Complete oxidation of volatile organic compounds at moderate temperatures. In Hazardous Materials: Types, Risks and Control. Brar SK, Ed. New York:Nova Science Publishers, 2011: 424-431.
[13]
Yasuda K, Yoshimura A, Katsuma A, et al. Low-temperature complete combustion of volatile organic compounds over novel Pt/CeO2–ZrO2–SnO2/γ-Al2O3 catalysts. B Chem Soc Jpn 2012, 85:522-526.
[14]
Suzuki H. Recovery of hydrocarbons from natural gas. Oil Gas Business Environ Res 1978, 11:95-103.
[15]
Hereijgers BPC, Weckhuysen BM. Aerobic oxidation of cyclohexane by gold-based catalysts: New mechanistic insight by thorough product analysis. J Catal 2010, 270:16-25.
[16]
Tolman CA, Druliner JD, Nappa MJ, et al. Alkane oxidation studies in du Pont's central research department. In Activation and Functionalization of Alkanes. Hill CL, Ed. Chichester:Wiley, 1989: 303-360.
[17]
Sheldon RA, Kochi JK. Metal-Catalyzed Oxidations of Organic Compounds. New York:Academic Press, 1981.
[18]
Ramanathan A, Hamdy MS, Parton R, et al. Co-TUD-1 catalysed aerobic oxidation of cyclohexane. Appl Catal A: Gen 2009, 355:78-82.
[19]
Xu LX, He CH, Zhu MQ, et al. A highly active Au/Al2O3 catalyst for cyclohexane oxidation using molecular oxygen. Catal Lett 2007, 114:202-205.
[20]
Pohorecki R, Bałdyga J, Moniuk W, et al. Kinetic model of cyclohexane oxidation. Chem Eng Sci 2001, 56:1285-1291.
Publication history
Copyright
Acknowledgements
Rights and permissions

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.

Rights and permissions

Open Access: This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.

Return