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

doi:10.1016/j.cjche.2017.10.005

Abstract

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

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

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.

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.

References

[1] H.K. Fauske, Revisiting DIERS' two-phase methodology for reactive systems twenty years later, Process. Saf. Prog. 25(3) (2006) 180-188.

[2] K.R. Westerterp, E.J. Molga, Safety and runaway prevention in batch and semibatch reactors-a review, Chem. Eng. Res. Des. 84(7) (2006) 543-552.

[3] H.G. Fisher, Emergency relief system design using DIERS technology:the Design Institute for Emergency Relief Systems (DIERS) project manual, Emergency Relief System Design Using DIERS Technology 2010, pp. 1-49.

[4] E. Wilcock, R.L.A. Rogers, Review of the phi factor during runaway conditions, J. Loss Prev. Process Ind. 10(5) (1997)289-302.

[5] J.C. Leung, H.K. Fauske, Runaway system ch aracterization and vent sizing based on DIERS methodology, Plant/Oper. Prog. 6(2) (1987) 77-83.

[6] D.I. Townsend, J.C. Tou, Thermal hazard evaluation by an accelerating rate calorimeter, Thermochim. Acta 37(1) (1980) 1-30.

[7] A.A. Kossoy, J. Singh, E.Y. Koludarova, Mathematical methods for application of experimental adiabatic data-an update and extension, J. Loss Prev. Process Ind. 33(2015) 88-100.

[8] M. Steensma, K.R. Westerterp, Thermally safe operation of a semibatch reactor for liquid-liquid reactions. Slow reactions, Chem. Eng. Technol. 14(6) (1991) 367-375.

[9] R. Widell, H.T. Karlsson, Autocatalytic behaviour in esterification between anhydrides and alcohols, Thermochim. Acta 447(1) (2006) 57-63.

[10] R. Reisen, B. Grob, Reaction calorimetry in chemical process development, Swiss Chem. 7(5) (1985) 39-43.

[11] C.F. Askonas, J.P. Burelbach, J.C. Leung, The versatile VSP2:a tool for adiabatic thermal analysis and vent sizing applications, In:28th Annual North American Thermal Analysis Society (NATAS) Conference, Orlando, Florida October 2000, pp. 4-6.

[12] A. Crevatin, F. Mascarello, B. Leuthe, B. Minder, I. Kikic, Kinetic investigations of a Ketonization reaction using reaction calorimetry, Ind. Eng. Chem. Res. 38(1999) 4629-4633.

[13] S. Leveneur, M. Thones, J.-P. Hebert, B. Taouk, T. Salmi, From kinetic study to thermal safety assessment:application to peroxyformic acid synthesis, Ind. Eng. Chem. Res. 51(2012) 13999-14007.

[14] V. Casson, D.G. Lister, M.F. Milazzo, et al., Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol, J. Loss Prev. Process Ind. 25(1) (2012)209-217.

[15] Y.S. Duh, C.C. Hsu, C.S. Kao, et al., Applications of reaction calorimetry in reaction kinetics and thermal hazard evaluation, Thermochim. Acta 285(1) (1996) 67-79.

[16] L. Friedel, G. Wehmeier, Modelling of the vented methanol/acetic anhydride runaway reaction using SAFIRE, J. Loss Prev. Process Ind. 4(2) (1991) 110-119.

[17] T.K. Wright, R.L. Rogers, Adiabatic dewar calorimeter, In:IChemE Symposium Series, 97, 1986, p. 121.

[18] L. Balland, N. Mouhab, J.M. Cosmao, et al., Kinetic parameter estimation of solventfree reactions:application to esterification of acetic anhydride by methanol, Chem. Eng. Process. Process Intensif. 41(5) (2002) 395-402.

[19] H.Y. Wei, Z.C. Guo, L. Hao, et al., Identification of the kinetic parameters and autocatalytic behavior in esterification via isoperibolic reaction calorimetry, Org. Process. Res. Dev. 20(8) (2016) 1416-1423.

[20] E. Pollak, P. Talkner, Reaction rate theory:what it was, where is it today, and where is it going? Chaos 15(2) (2005) 026116.

[21] K.J. Laidler, The development of the Arrhenius equation, J. Chem. Educ. 61(6) (1984) 494.

[22] D.I.F. Stoessel, Thermal Safety of Chemical Processes:Risk Assessment and Process Design, 2008.

[23] H.L. Anderson, A. Kemmler, R. Strey, Comparison of different non-linear evaluation methods in thermal analysis, Thermochim. Acta 271(95) (1996)23-29.

[24] H.J. Flammersheim, J.R. Opfermann, Kinetic evaluation of DSC curves for reacting systems with variable stoichiometric compositions, Thermochim. Acta 388(1-2) (2002) 389-400.

[25] D.M. Himmelblau, Applied Nonlinear Programming, 1972.

[26] M. Mehrvar, W.A. Anderson, M. Moo-Young, et al., Non-linear parameter estimation for a dynamic model in photocatalytic reaction engineering, Chem. Eng. Sci. 55(21) (2000) 4885-4891.

[27] S. Vyazovkin, A.K. Burnham, J.M. Criado, et al., ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data, Thermochim. Acta 520(1) (2011) 1-19.