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Research Article | Open Access

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

Nobuhito IMANAKA(), Toshiyuki MASUI, Kazuya JYOKO
Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
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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 materialsoxidationcyclohexaneKA-oilcatalyst

References

[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[10]
Imanaka N, Masui T. Advanced materials for environmental catalysts. Chem Rec 2009, 9:40-50.
Crossref Google Scholar
[11]
Imanaka N, Masui T, Yasuda K. Environmental catalysts for complete oxidation of volatile organic compounds and methane. Chem Lett 2011, 40:780-785.
Crossref Google Scholar
[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.
Crossref Google Scholar
[14]
Suzuki H. Recovery of hydrocarbons from natural gas. Oil Gas Business Environ Res 1978, 11:95-103.
Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[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.
Crossref Google Scholar
[20]
Pohorecki R, Bałdyga J, Moniuk W, et al. Kinetic model of cyclohexane oxidation. Chem Eng Sci 2001, 56:1285-1291.
Crossref Google Scholar
Journal of Advanced Ceramics
Volume 4 Issue 2,
June 2015
Pages 111-117
DOI: 10.1007/s40145-015-0138-0
Cite this article:
IMANAKA N, MASUI T, JYOKO K. Selective liquid phase oxidation of cyclohexane over Pt/CeO2–ZrO2–SnO2/SiO2 catalysts with molecular oxygen. Journal of Advanced Ceramics, 2015, 4(2): 111-117. https://doi.org/10.1007/s40145-015-0138-0
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10.1007/s40145-015-0138-0.T001Catalytic performance of catalysts at 130 ℃ for 7 h in 0.5 MPa air atmosphere

Catalyst*Surface area (m2·g−1)Amount of CO chemisorption (μmol·g−1)Total amount of Pt atoms (μmol·g−1)Dispersion (%)Conversion (mol%)KA-oil yield (mmol)KA-oil synthesis rate†(mmol·g−1·h−1)Selectivity (mol%)TOF§ (h−1)
CyclohexanolCyclohexanone
Pt(1)/CZS/SiO232211.451.322.215.07.8411258.729.39845
Pt(3)/CZS/SiO232033.215421.617.58.8612756.029.23810
Pt(5)/CZS/SiO231348.925619.124.111.917155.228.23485
Pt(7)/CZS/SiO229029.13598.115.57.7711155.429.03820
Pt(10)/CZS/SiO227536.45137.112.66.429255.630.12518

*Pt content was determined by XRF. †Reaction conditions: 10 mg catalyst, 5.0 g cyclohexane, 130 ℃, 0.5 MPa, and 7 h. §TOF was calculated from the rate of KA-oil (cyclohexanol and cyclohexanol) synthesis divided by the amount of CO molecules chemisorbed on the Pt surfaces.

10.1007/s40145-015-0138-0.T002Catalytic performance of the Pt(5)/CZS/SiO2 catalyst under various reaction conditions

Pressure (MPa)Temperature (℃)Reaction time (h)Conversion (mol%)KA-oil yield (mmol)KA-oil synthesis rate‡ (mmol·g−1·h−1)Selectivity(mol%)TOF§ (h−1)
Cyclo-hexanolCyclo-hexanone
0.31307000000
0.413.26.749656.629.41968
0.4519.79.9014155.329.32889
0.524.111.917155.228.23485
0.5525.311.917051.327.83470
0.625.89.8114040.024.02863
0.5120711.55.948556.530.41733
13024.111.917155.228.23485
14024.710.515051.020.63066
15024.810.214648.820.52980
0.51303000000
511.15.6411354.131.52306
724.111.917155.228.23485
924.59.1010139.123.42065
1225.58.367035.619.61424

‡Reaction conditions: 10 mg catalyst, 5.0 g cyclohexane. §TOF was calculated from the rate of KA-oil (cyclohexanol and cyclohexanol) synthesis divided by the number of CO molecules chemisorbed on the Pt surfaces.