Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics

doi:10.1016/j.cjche.2017.10.005

摘要/Abstract

摘要： In the field of adiabatic correction for complex reactions, a simple one-stage kinetic model was used to estimate the real reaction kinetics. However, this assumption simplified the real process, inevitably generated inaccurate or even unsafe results. Therefore, it was necessary to find a new correction method for complex reactions. In this work, esterification of acetic anhydride by methanol was chosen as an object reaction of study. The reaction was studied under different conditions by Reaction Calorimeter (RC1). Then, Thermal Safety Software (TSS) was used to establish the kinetic model and estimate the parameters, where, activation energies for three stages were 67.09, 81.02, 73.77 kJ·mol^-1 respectively, and corresponding frequency factors in logarithmic form were 16.05, 19.59, 15.72 s^-1. In addition, two adiabatic tests were performed by Vent Sizing Package2 (VSP2). For accurate correction of VSP2 tests, a new correction method based on Enhanced Fisher method was proposed. Combined with kinetics, adiabatic correction of esterification reaction was achieved. Through this research, accurate kinetic parameters for a three-step kinetic model of the esterification reaction were acquired. Furthermore, the correlation coefficients between simulated curves and corrected curves were 0.976 and 0.968, which proved the accuracy of proposed new adiabatic correction method. Based on this new method, conservative corrected results were able to be acquired and be applied in safety assessment.

关键词: Adiabatic correction, Kinetics, New method, Complex reaction, Esterification, Model reaction

Abstract: In the field of adiabatic correction for complex reactions, a simple one-stage kinetic model was used to estimate the real reaction kinetics. However, this assumption simplified the real process, inevitably generated inaccurate or even unsafe results. Therefore, it was necessary to find a new correction method for complex reactions. In this work, esterification of acetic anhydride by methanol was chosen as an object reaction of study. The reaction was studied under different conditions by Reaction Calorimeter (RC1). Then, Thermal Safety Software (TSS) was used to establish the kinetic model and estimate the parameters, where, activation energies for three stages were 67.09, 81.02, 73.77 kJ·mol^-1 respectively, and corresponding frequency factors in logarithmic form were 16.05, 19.59, 15.72 s^-1. In addition, two adiabatic tests were performed by Vent Sizing Package2 (VSP2). For accurate correction of VSP2 tests, a new correction method based on Enhanced Fisher method was proposed. Combined with kinetics, adiabatic correction of esterification reaction was achieved. Through this research, accurate kinetic parameters for a three-step kinetic model of the esterification reaction were acquired. Furthermore, the correlation coefficients between simulated curves and corrected curves were 0.976 and 0.968, which proved the accuracy of proposed new adiabatic correction method. Based on this new method, conservative corrected results were able to be acquired and be applied in safety assessment.

Key words: Adiabatic correction, Kinetics, New method, Complex reaction, Esterification, Model reaction

Ze Dong, Liping Chen, Yingying Ma, Haoliang Peng, Wanghua Chen. Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics[J]. Chinese Journal of Chemical Engineering, 2018, 26(9): 1954-1959.

Ze Dong, Liping Chen, Yingying Ma, Haoliang Peng, Wanghua Chen. Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics[J]. Chin.J.Chem.Eng., 2018, 26(9): 1954-1959.

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