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Transactions of Tianjin University

, Volume 25, Issue 1, pp 52–65 | Cite as

Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed by Mn–Mo Oxide

  • Wang Li
  • Qingjun Zhang
  • Aiwu ZengEmail author
Research Article
  • 91 Downloads

Abstract

In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest (≈ 81 kJ mol−1), while that of benzyl alcohol oxidation to benzaldehyde was the lowest (≈ 57 kJ mol−1). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower (≈ 1.9 kJ mol−1) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism (Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed (ΔHads,Oxy ≈ − 15 kJ mol−1, ΔHads,Bald ≈ − 30 kJ mol−1), but showed strong mobility (ΔSads,Oxy ≈ − 22 J mol−1 K−1), ΔSads,Bald ≈ − 39 J mol−1 K−1). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.

Keywords

Liquid phase Oxidation of toluene Heterogeneous catalyst Benzaldehyde Kinetics LH-OS-ND mechanism 

Notes

Acknowledgements

This study was supported by the National Natural Science Foundation of China (No. 21376163).

Supplementary material

12209_2018_146_MOESM1_ESM.doc (3.9 mb)
Supplementary material 1 (DOC 4021 kb)

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Copyright information

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina

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