Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

doi:10.1016/S1004-9541(14)60071-9

摘要/Abstract

摘要： Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

关键词: kinetic control, oxygen transfer limitations, catalysis, toluene, oxidation, porphyrin

Abstract: Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

Key words: kinetic control, oxygen transfer limitations, catalysis, toluene, oxidation, porphyrin

罗伟平, 刘大为, 孙俊, 邓伟, 盛文兵, 刘强, 郭灿城. Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene[J]. Chinese Journal of Chemical Engineering, 2014, 22(5): 509-515.

LUO Weiping, LIU Dawei, SUN Jun, DENG Wei, SHENG Wenbing, LIU Qiang, GUO Cancheng. Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene[J]. Chin.J.Chem.Eng., 2014, 22(5): 509-515.

参考文献

1 Borgaonkar, H.V., Raverkar, S.R., Chandalia, S.B., "Liquid phase oxidation of toluene to benzaldehyde by air", Ind. Eng. Chem. Prod. Res. Dev., 23 (3), 455-458 (1984).

2 Kirk, O., Kirk-Othmer Encyclopedia of Chemical Technology, Wiley, New York (2004).

3 Kaeding, W.W., "How Dow makes phenol from toluene", Hydrocarbon Process. Pet. Refiner., 43 (11), 173-176 (1964).

4 Messina, G., "Upgrade toluene to benzoic acid", Hydrocarbon Process. Pet. Refiner., 43 (11), 191-192 (1964).

5 Morimoto, T., Ogata, Y., "Kinetics of the autoxidation of toluene catalysed by cobaltic acetate. Part II. Effects of benzaldehyde, cobalt, and substituent", J. Chem. Soc. B, 12, 1353-1357 (1967).

6 Tang, S.W., Shen, W., Liang, B., "Influences of the [Co²⁺]/[Co³⁺] ratio on the process of liquid-phase oxidation of toluene by air", Chin. J. Chem. Eng., 17 (4), 613-617 (2009).

7 Zhang, Y.K., Li, C.F., He, X.R., Chen, B.Z., "Simulation and optimization in the process of toluene liquid-phase catalytic oxidation", Chin. J. Chem. Eng., 16 (1), 36-38 (2008).

8 Kantam, M.L., Sreekanth, P., Rao, K.K., Kumar, T.P., Rao, B.P.C., Choudary, B.M., "An improved process for selective liquid-phase air oxidation of toluene", Catal. Lett., 81 (3), 223-232 (2002).

9 Partenheimer, W., "Methodology and scope of metal/bromide autoxidation of hydrocarbons", Catal. Today, 23 (2), 69-158 (1995).

10 Guo, C.C., Liu, Q., Wang, X.T., Hu, H.Y., "Selective liquid phase oxidation of toluene with air", Appl. Catal., A, 282 (1-2), 55-59 (2005).

11 Hu, H.Y., Guo, C.C., "Catalysis of ?-oxo-bis[porphyriniron(III)] for toluene oxidation with molecular oxygen", J. Porphyrins Phthalocyanines, 10 (7), 948-952 (2006).

12 Li, Y.F., Yan, X.H., Jiang, G.F., Liu, Q., Song, J.X., Guo, C.C., "Toluene oxyfunctionalization with air over metalloporphyrins and reaction condition optimization", Chin. J. Chem. Eng., 15 (3), 453-457 (2007).

13 Hoorn, J.A.A., Van, S.J., Versteeg, G.F., "Modelling toluene oxidations incorporation of mass transfer phenomena", Chem. Eng. Res. Des., 83 (A2), 187-195 (2005).

14 Tang, S.W., Liang, B., "Kinetics of the liquid-phase oxidation of toluene by air", Ind. Eng. Chem. Res., 46 (20), 6442-6448 (2007).

15 Bhattacharya, D., Guha, D.K., Roy, A.N., "Liquid phase air oxidation of toluene to benzoic acid. II. Kinetics and mechanism", Chem. Age India., 24 (2), 87-90 (1973).

16 Morimoto, T., Ogata, Y., "Kinetics of the autoxidation of toluene catalysed by cobaltic acetate", J. Chem. Soc. B, 1, 62-64 (1967).

17 Millsa, P.L., Chaudhari, R.V., "Reaction engineering of emerging oxidation processes", Catal. Today, 48 (1-4), 17-29 (1999).

18 Roby, A.K., Kingsley, J.P., "Oxide safely with pure oxygen", Chemtech, 26 (2), 39-46 (1996).

19 Tan, P.H., Tang, S.W., Liang, B., "Kinetic models for liquid-phase catalytic oxidation of toluene to benzoic acid with pure oxygen", Chem. Eng. Commun., 197, 953-962 (2010).

20 Suresh, A.K., Sharma, M.M., Sridhar, T., "Engineering aspects of industrial liquid-phase air oxidation of hydrocarbons", Ind. Eng. Chem. Res., 39 (11), 3958-3997 (2000).

21 Guo, C.C., "Synthesis of [mu]-oxo-bisiron(III)porphyrin compounds and their catalysis for cyclohexane hydroxylation", J. Catal., 178 (1), 182-187 (1998).

22 Guo, C.C., Li, H.P., Xu, J.X., "Study of synthesis of [mu]-oxo- bismanganese(III) porphyrin compounds and their catalysis of cyclohexane oxidation by PhIO", J. Catal., 185 (2), 345-351 (1999).

23 Jiang, Q., Hu, H.Y., Guo, C.C., Liu, Q., Song, J.X., Li, Q.H., "Aerobic liquid-phase oxidation of p-xylene over metalloporphyrins", J. Porphyrins Phthalocyanines, 11 (7), 524-530 (2007).

24 Jiang, Q., Xiao, Y., Tan, Z., Liu, Q., Guo, C.C., "Aerobic oxidation of p-xylene over metalloporphyrin and cobalt acetate: Their synergy and mechanism", J. Mol. Catal. A Chem., 285 (1-2), 162-168 (2008).

25 Sridhar, T., Potter, O.E., "Interfacial areas in gas-liquid stirred vessels", Chem. Eng. Sci., 35 (3), 683-695 (1980).

26 Sridhar, T., Potter, O.E., "Interfacial area measurements in gas-liquid agitated vessels", Chem. Eng. Sci., 33 (10), 1347-1353 (1978).

27 Suresh, A.K., Sridhar, T., Potter, O.E., "Autocatalytic oxidation of cyclohexane-modelling reaction kinetics", AIChE J., 34 (1), 69-80 (1988).

28 Suresh, A.K., Sridhar, T., Potter, O.E., "Mass transfer and solubility in autocatalytic oxidation of cyclohexane", AIChE J., 34 (1), 55-68 (1988).

29 Meunier, B., "Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage", Chem. Rev., 92 (6), 1411-1456 (1992).

30 Kadish, K.M., Smith, K.M., Guilard, R., The Porphyrin Handbook, Academic Press, New York (2000).

31 Lyons, J.E., Ellis, P.E., Myers, H.K., "Halogenated metalloporphyrin complexes as catalysts for selective reactions of acyclic alkanes with molecular oxygen", J. Catal., 155 (1), 59-73 (1995).

32 Ryszard, P., Jerzy, B., "Kinetic model of cyclohexane oxidation", Chem. Eng. Sci., 56 (4), 1285-1291 (2001).

[1]	Baoyu Liu, Feng Xiong, Jianwen Zhang, Manna Wang, Yi Huang, Yanxiong Fang, Jinxiang Dong. Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites[J]. 中国化学工程学报, 2023, 60(8): 1-7.
[2]	Xun Tao, Fan Zhou, Xinlei Yu, Songling Guo, Yunfei Gao, Lu Ding, Guangsuo Yu, Zhenghua Dai, Fuchen Wang. Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide: An experimental and kinetic modeling[J]. 中国化学工程学报, 2023, 59(7): 105-117.
[3]	Fei Li, Xuemei Wang, Pengze Zhang, Qinqin Wang, Mingyuan Zhu, Bin Dai. Nitrogen and phosphorus co-doped activated carbon induces high density Cu⁺ active center for acetylene hydrochlorination[J]. 中国化学工程学报, 2023, 59(7): 193-199.
[4]	Tingjun Fu, Ran Wang, Kun Ren, Liangliang Zhang, Zhong Li. Intensified shape selectivity and alkylation reaction for the two-step conversion of methanol aromatization to p-xylene[J]. 中国化学工程学报, 2023, 59(7): 240-250.
[5]	Zijie Zhang, Qianyu Zha, Ying Liu, Zhibing Zhang, Jia Liu, Zheng Zhou. Study on the epoxidation of olefins with H₂O₂ catalyzed by biquaternary ammonium phosphotungstic acid[J]. 中国化学工程学报, 2023, 58(6): 146-154.
[6]	Haodi Tan, Minjiao Yang, Yingquan Chen, Xu Chen, Francesco Fantozzi, Pietro Bartocci, Roman Tschentscher, Federica Barontini, Haiping Yang, Hanping Chen. Preparation of aromatic hydrocarbons from catalytic pyrolysis of digestate[J]. 中国化学工程学报, 2023, 57(5): 1-9.
[7]	Chenyang Zhao, Yinhan Cheng, Guangfei Qu, Yongheng Yuan, Fenghui Wu, Ye Liu, Shan Liu, Junyan Li, Ping Ning. High-performance liquid-phase catalytic purification of phosphine in tail gas using Pd(II)/Cu(II) composite[J]. 中国化学工程学报, 2023, 57(5): 98-108.
[8]	Bingxiao Feng, Lining Hao, Chaoting Deng, Jiaqiang Wang, Hongbing Song, Meng Xiao, Tingting Huang, Quanhong Zhu, Hengjun Gai. A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater[J]. 中国化学工程学报, 2023, 57(5): 338-348.
[9]	Shengfeng Luo, Song Zhang, Yiping Zeng, Hui Zhang, Lili Zheng, Zhaopeng Xu. Study on oxygen transport and titanium oxidation in coating cracks under parallel gas flow based on LBM modelling[J]. 中国化学工程学报, 2023, 56(4): 15-24.
[10]	Yuxi Chai, Yanan Zhang, Yannan Tan, Zhiwei Li, Huangzhao Wei, Chenglin Sun, Haibo Jin, Zhao Mu, Lei Ma. Life cycle assessment of high concentration organic wastewater treatment by catalytic wet air oxidation[J]. 中国化学工程学报, 2023, 56(4): 80-88.
[11]	Peiyin Chen, Yanxiong Fang, Kaihong Xie, Yao Chen, Yang Liu, Hongliang Zuo, Weijian Lu, Baoyu Liu. Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene[J]. 中国化学工程学报, 2023, 56(4): 152-159.
[12]	Tinghao Jia, Yunbo Yu, Qing Liu, Yao Yang, Ji-Jun Zou, Xiangwen Zhang, Lun Pan. Theoretical and experimental study on the inhibition of jet fuel oxidation by diarylamine[J]. 中国化学工程学报, 2023, 56(4): 225-232.
[13]	Juan Du, Aibing Chen, Senlin Hou, Xueqing Gao. Self-deposition for mesoporous carbon nanosheet with supercapacitor application[J]. 中国化学工程学报, 2023, 55(3): 34-40.
[14]	Da Ke, Minjia Wang, Jiancheng Ruan, Xinzhi Chen, Shaodong Zhou. Efficient, continuous oxidation of durene to pyromellitic dianhydride mediated by a V-Ti-P ternary catalyst: The remarkable doping effect[J]. 中国化学工程学报, 2023, 55(3): 156-164.
[15]	Qiongna Xiao, Yuyan Jiang, Weiqiang Yuan, Jingjing Chen, Haohong Li, Huidong Zheng. Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism[J]. 中国化学工程学报, 2023, 55(3): 192-201.