KINETIC RESEARCH AND MODELING OF BENZOIC ACID ESTERIFICATION PROCESS
DOI:
https://doi.org/10.15421/jchemtech.v29i4.241445Keywords:
benzoic acid, 1-butyl alcohol, butyl benzoate, esterification, kinetic, p-toluenesulfonic acid, modelingAbstract
The kinetic regularities of benzoic acid esterification with 1-butyl alcohol catalyzed by p-toluenesulfonic acid under stationary conditions have been studied. The study shows that the reaction has the first order with respect to benzoic acid. It is proposed a method for calculating the forward and reverse reaction constants, and the equilibrium constant using the determined effective rate constant of the esterification reaction. The preexponential factors and activation energies of the forward and reverse reactions as well as the thermal effect and the entropy change of the esterification reaction have been calculated. In particular, the thermal effect of benzoic acid esterification reaction with 1-butyl alcohol at a temperature of 365.2–389.4 K is 622 J∙mol-1, and the activation energies of the forward and reverse reactions are 58.40 and 57.70 kJ∙mol-1, respectively. The calculated kinetic characteristics of the esterification reaction were used in mathematical modeling of the butyl benzoate obtaining process under nonstationary conditions. Taking into account the kinetic characteristics of the reactions and the stages peculiarities of the butyl benzoate obtaining process the calculation of the change in the benzoic acid conversion over time was performed. The study shows that under optimal conditions the benzoic acid conversion in 120 min reaches 92 %. The use of the experimental results and the created mathematical model of benzoic acid esterification process with 1-butyl alcohol makes it possible to calculate of kinetic curves of the reagent consumption under nonstationary conditions. The experimentals can be used to improve the technological process of the butyl benzoate manufacture in the industry.
References
Referens
Feng, Y., Zhang, A. (2017). A floral fragrance, methyl benzoate, is an efficient green pesticide. Sci. Rep., 7, 42168. https://doi.org/10.1038/srep42168
del Olmo, A., Calzada, J., Nunez, M. (2017). Benzoic acid and its derivatives as naturally occurring compounds in foods and as additives: Uses, exposure, and controversy. Crit. Rev. Food Sci. Nutr., 57, 3084–3101. https://doi.org/10.1080/10408398.2015.1087964
Melnyk, Yu., Melnyk, S., Palyukh, Z., Dzinyak, B. (2018). Research into transesterification of triglycerides by aliphatic alcohols C2–C4 in the presence of ionites. East.-Eur. J. Enterp. Technol., 1/6(94), 10-16. https://doi.org/10.15587/1729-4061.2018.122938
Zhang, Z., Jiang, P., Liu, D., Feng, S., Leng, Y., Zhang P., Haryono, A., Lic, Z., Lic, Y. (2021). Synthesis of novel plasticizer ester end-capped oligomeric lactic acid and its plasticizing performance in poly(vinyl chloride). New J. Chem., 45, 11371-11379. https://doi.org/10.1039/D1NJ01604K
Tajti, A., Tуth, N., Balin, E., Keglevich, G. (2018). Esterification of benzoic acid in a continuous flow microwave reactor. J. Flow Chem., 8, 11-19. https://doi.org/10.1007/s41981-018-0001-x
Lilja, J., Murzin, D. Yu., Salmi, T., Aumo, J., Mäki-Arvela, P., Sundell, M. (2002). Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the Taft equation. J. Mol. Catal. A: Chem., 182-183, 555-563. https://doi.org/10.1016/S1381-1169(01)00495-2
Otera, J., Nishikido, J. (2010). Esterification: Methods Reactions, and Applications (2nd Ed.), Wiley-VCH, Weinheim.
Melnyk, S., Melnyk, Y., Nykulyshyn, I., Shevchuk, L. (2017). Research into esterification of mixture of lower dicarboxylic acids by 2-ethylhexan-1-ol in the presence of p-toluensulfonic acid. East.-Eur. J. Enterp. Technol., 6(6-90), 10-16. https://doi.org/10.15587/1729-4061.2017.114324
Melnyk, S., Reutskyy, V. (2014). Technological aspects of dicarboxylic acids esterification in the presence of aprotic catalysts. Chem. Chem. Technol., 8(1), 93-97.
Melnyk, S. (2013). Perfluorooxasulphonates of metals - the catalysts of esters manufacture. Chem. Chem. Technol., 7(3), 257-260.
Čebular, K., Božić, B., Stavber, S. (2018). Esterification of aryl/alkyl acids catalysed by N-bromosuccinimide under mild reaction conditions. Molecules, 23(9), 2235-2251. https://doi.org/10.3390/molecules23092235
Abd Manan, F. M., Attan, N., Zakaria Z., Keyon A. S. A., Wahab R. A. (2018). Enzymatic esterification of eugenol and benzoic acid by a novel chitosan-chitin nanowhiskers supported Rhizomucor miehei lipase: Process optimization and kinetic assessments. Enzyme Microb. Technol., 108, 42-52. https://doi.org/10.1016/j.enzmictec.2017.09.004
Cai, Y. Q., Yu, G. Q., Liu, C. D., Xu, Y. Y., Wang, W. (2012). Imidazolium ionic liquid-supported sulfonic acids: Efficient and recyclable catalysts for esterification of benzoic acid. Chin. Chem. Lett., 23, 1-4. https://doi.org/10.1016/J.CCLET.2011.09.016
Buluklu, A. D., Sert, E., Karakus, S., Atalay, F. S. (2014). Development of kinetic mechanism for the esterification of acrylic acid with hexanol catalyzed by ion-exchange resin. Int. J. Chem. Kinet., 46, 197-205. https://doi.org/10.1002/kin.20841
Sert, E., Atalay, F. S. (2012). Esterification of acrylic acid with different alcohols catalyzed by zirconia supported tungstophosphoric acid. Ind. Eng. Chem. Res., 51(19), 6666-6671. https://doi.org/10.18466/cbayarfbe.370364
Singh, C., Mittal, S. K., Kaur, N. (2015) Zirconium based ion exchangers as catalysts in esterification reactions of benzoic acid. Asian J. Chem., 27(8), 3035-3038. https://dx.doi.org/10.14233/ajchem.2015.18822
da Silva, M. J., Ayala, D. A. M. (2016) Unravelling transition metal-catalyzed terpenic alcohol esterification: a straightforward process for the synthesis of fragrances. Catal. Sci. Technol., 6, 3197-3207. https://dx.doi.org/10.1039/C5CY01538C
Rajabi, F., Abdollahi, M., Luque, R. (2016). Solvent-free esterification of carboxylic acids using supported iron oxide nanoparticles as an efficient and recoverable catalyst, Materials, 9(7), 557-565. https://doi.org/10.3390/ma9070557
Melnyk, S., Dzinyak, B. (2015). Selectivity of formation and yield of dicarboxylic acid mono- and diesters under stationary conditions. Chem. Chem. Technol., 9(3), 325-332. https://doi.org/10.23939/chcht09.03.325
Pipus, G., Plazl, I., Koloini, T. (2000). Esterification of benzoic acid in microwave tubular flow reactor. Chem. Eng. J., 7, 239-245. https://doi.org/10.1016/S1385-8947(99)00171-0
Sert, E., Atalay, F. S. (2017). Application of green catalysts for the esterification of benzoic acid with different alcohols. Celal Bayar Üniversity Journal of Science, 13(4), 907-912. https://doi.org/10.18466/cbayarfbe.370364
Marziano, N. C., Tortato, C. Ronchin, L., Bianchi, C. (2000). On the acidity of liquid and solid acid catalysts. Part 3. Esterification of benzoic and mesitoic acids. Catal. Lett., 64, 15-22. https://doi.org/10.1023/A:1019010230769
Barbosa, S. L., Ottone, M., Santos, M. C., Junior, G. C., Lima, C. D., Glososki, G. C., Lopes, N. P., Klein, S. I. (2015). Benzyl benzoate and dibenzyl ether from of benzoic acid and benzyl alcohol under microwave irradiation using a SiO2-SO3H catalyst. Catal. Commun., 68, 97-100. http://dx.doi.org/10.1016/j.catcom.2015.04.033
Pečar, D., Goršek, A. (2018). Kinetic modeling of benzoic acid esterification using functionalized silica gel. Chem. Eng. Commun., 205(8), 1034-1040. https://doi.org/10.1080/00986445.2018.1428960
Wu, M., Guo, J., Li, Y., Zhang, Y. (2013). Esterification of benzoic acid using Ti3AlC2 and SO42−/Ti3AlC2 ceramic as acid catalysts. Ceram. Int., 39, 9731-9736. http://dx.doi.org/10.1016/j.ceramint.2013.04.077
Lee, M. J., Chou, P. L., Lin, H. (2005). Kinetics of synthesis and hydrolysis of ethyl benzoate over Amberlyst-39. Ind. Eng. Chem. Res., 44(4), 725-732. https://doi.org/10.1021/ie049437w
Tiwari, R., Rahman, A., Bhat, N. S., Onkarappa, S. B., Mal, S. S., Dutta, S. (2019). Efficient preparation of alkyl benzoates by heteropolyacid-catalysed esterification of benzoic acid under solvent-free condition. ChemistrySelect, 4, 9119-9123. https://doi.org/10.1002/slct.201902208
Xue, J., Zeng, Z., Xue, W., Yang, H. (2018). Kinetics of esterification of benzoic acid and isoamyl alcohol catalyzed by p-toluenesulfonic acid. Can. J. Chem. Eng., 9999, 1-7. https://doi.org/10.1002/cjce.23158
Standard ASTM. (2021). Standard test method for acid and base number by color-indicator titration. (ASTM D974-21.
Downloads
Published
Issue
Section
License
Copyright (c) 2022 Днипровский национальный университет имени Олеся Гончара
This work is licensed under a Creative Commons Attribution 4.0 International License.
- Authors reserve the right of attribution for the submitted manuscript, while transferring to the Journal the right to publish the article under the Creative Commons Attribution License. This license allows free distribution of the published work under the condition of proper attribution of the original authors and the initial publication source (i.e. the Journal)
- Authors have the right to enter into separate agreements for additional non-exclusive distribution of the work in the form it was published in the Journal (such as publishing the article on the institutional website or as a part of a monograph), provided the original publication in this Journal is properly referenced
- The Journal allows and encourages online publication of the manuscripts (such as on personal web pages), even when such a manuscript is still under editorial consideration, since it allows for a productive scientific discussion and better citation dynamics (see The Effect of Open Access).
