A study of butyl acetate synthesis. 4. reaction kinetics
Estudio de la síntesis de acetato de butilo. 4. Cinética de reacción
DOI:
https://doi.org/10.15446/ing.investig.v26n2.14734Keywords:
ion exchange resins, esterification, butyl acetate, kinetics (en)resinas de intercambio, esterificación, acetato de butilo, cinética (es)
Downloads
This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (Patm =0.76 Bar), using an ion exchange resin (Lewatit K-2431) as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w) temperature (73°C, 80°C, 87°C) and molar ratio (1:2, 1:1, 2:1 acid/ alcohol) on reaction rate was carried out and both LHHW and pseudo-homogeneous kinetic expressions were obtained, these being in good agreement with the experimental data.
En este trabajo se adelantó un estudio de la reacción de esterificación de ácido acético y n-butanol en fase liquida (Patm = 0,76 Bar), utilizando unas resinas de intercambio catiónico (Lewatit K-2431) como catalizador. Se estableció la ausencia de efectos de transferencia de masa dentro y fuera de las partículas de catalizador en las condiciones estudiadas. Se efectuaron ensayos para determinar la influencia de la carga del catalizador (0.5 %, 1%, 2% p/p), la temperatura (73°C, 80°C, 87°C) y la relación molar de alimentación (ácido/alcohol 1:2, 1:1, 2:1) sobre la velocidad de la reacción, y se obtuvieron dos expresiones cinéticas del tipo LHHW y seudohomogéneo que representa adecuadamente los datos experimentales.
References
Agreda, V., Partin L., y Hebe, W., High-Purity Methyl Acetate via Reactive Distillation., Chem. Eng. Prog., Vol 86, 1990, pp. 40-46.
Al-Saadi, A., y Jetreys, G., Esterification of butanol in a two-phase liquid/liquid system., AIChE Journal, 27, 1981, pp. 754 - 773. DOI: https://doi.org/10.1002/aic.690270508
Altiokka, M., y Cytak, A., Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst., Applied Catalysis A: General, 239, 2003, pp. 141-148. DOI: https://doi.org/10.1016/S0926-860X(02)00381-2
Bayer AG., Bayer Catalyst K 2431, Product Information, Leverkusen - Germany, 2001.
Bayer AG., Catalysis and chemical processing with Lewatit®., Technical Information, Leverkusen - Germany, 2001.
Bevia, F, Prast, D., Gomis, V., y Varo, P, Quaternary liquid-liquid equilibrium: water - acetic acid - butanol n-butyacetate at 25 °C., Fluid Phase Equilibria, 18, 1984, pp. 171-183. DOI: https://doi.org/10.1016/0378-3812(84)87005-3
Bianchi, C., Ragaini, V., Pirola, C., y Carvoli, G., A new method to clean industrial water from acetic acid via esterification., Applied Catalysis B: Environmental, Vol 40, 2003, pp. 93 - 99. DOI: https://doi.org/10.1016/S0926-3373(02)00144-3
Cardona, C., Marulanda, V., y Young, D., Analysis of the environmental impact of butylacetate process through the WAR algorithm,. Chem. Eng. Sci., Vol. 59, 2004, pp. 5839-5845. DOI: https://doi.org/10.1016/j.ces.2004.06.043
Dhanuka, V., Malche, V., y Chandalia, B., Kinetics of liquid phase esterification of carboxylic acid with alcohols in the presence of acid catalysts., Chem. Eng. Sci., Vol 32, 1957, pp. 551-556. DOI: https://doi.org/10.1016/0009-2509(77)87013-9
Chu, W., Hu, J., Xie, Z., y Chen Q., Design and Elaboration of New Solid Acids for the Synthesis of Butylacetate., Catalysis Today, 90, 2004, pp. 349 - 353. DOI: https://doi.org/10.1016/j.cattod.2004.04.046
Esquivel, M., y Bernardo-Gil, M., Liquid-liquid equilibria for the systems water - alcohols - acetic acid., Fluid Phase Equilibria, 57, 1990, pp. 307-316. DOI: https://doi.org/10.1016/0378-3812(90)85129-X
Gangadwala, J., Mankar, S., y Mahajani, S., Esterification of Acetic Acid with Butanol in the presence of Ion-exchange resins as Catalysts., Ind. Eng. Chem. Res., Vol 42, 2003, pp. 2146-2155. DOI: https://doi.org/10.1021/ie0204989
Gangadwala, J., Kienle, A., Stein, E., y Mahajani, S., Production of Butyl Acetate by Catalytic Distillation: Process Design Studies., Ind. Eng. Chem. Res., Vol 43, 2004, pp. 136-143. DOI: https://doi.org/10.1021/ie021011z
Giessler, S., Danilov, R., Pisarenko, R., Serafimov, L., Hasebe, S., y Hashimoto, II., Feasible Separation Modes for Various Reactive Distillation Systems., Ind. Eng. Chem. Res., 38, 1999, pp. 4060-4067. DOI: https://doi.org/10.1021/ie9900162
Groggins, PH., Procesos de Industriales de Síntesis Orgánica., Ed Gustavo Gili, Barcelona, 1953.
Hanika, J., Kolena, J., y Smejkal, Q., Butylacetate via reactive distillation - modelling and experiment., Chem. Eng. Sci., Vol 54, 1999, pp. 5205-5209. DOI: https://doi.org/10.1016/S0009-2509(99)00241-9
Lee, M., Wu, H., y Lin, H., Kinetics of Catalytic Esterification of Acetic Acid and Amyl Alcohol over Dowex., Ind. Eng. Chem. Res., Vol. 39, 2000, pp. 4094-4099. DOI: https://doi.org/10.1021/ie0000764
Lee, M., Chiu, J., y Lin, H., Kinetics of Catalytic Esterification of Propionic Acid and n-Butanol over Amberlyst 35., Ind. Eng. Chem. Res., Vol 41, 2002, pp. 2882-2887. DOI: https://doi.org/10.1021/ie0105472
Leyes, C., y Othmer, D., Continuous Esterification of Butanol and Acetic Acid, Kinetic and Distillation Considerations., Trans., Amer. Inst. Chem. Engrs., Vol 41, 1945, pp. 157-196.
Lilja, J., Aumo, J., Salmi. T., y Murzin, D., Kinetics of esterification of propanoic acid with methanol over a fibrous polymer-supported sulphonic acid catalyst., Applied Catalysis A: General, 228, 2002, pp. 253-267. DOI: https://doi.org/10.1016/S0926-860X(01)00981-4
Liu, O., Zhang, Z., y Cheng, H., Study on the coupling of esterification with pervaporation., Journal of Membrane Science, 182, 2001, pp. 173 - 181. DOI: https://doi.org/10.1016/S0376-7388(00)00568-8
Liu, O., y Chen, H., Modeling of esterification of acetic acid with n-butanol in the presence of Zr(SO4)2.4H2O coupled pervaporation., Journal of Membrane Science, 196, 2002, pp. 171 - 178. DOI: https://doi.org/10.1016/S0376-7388(01)00543-9
Löning S., Horts, C., y Hotfmann, U., Theoretical Investigation on the quaternary system n-butanol, butyl acetate, acetic acid and water., Chem. Eng. Tech., Vol 23, No. 9, 2000, pp. 789-793. DOI: https://doi.org/10.1002/1521-4125(200009)23:9<789::AID-CEAT789>3.0.CO;2-E
Mazzotti, M., Neri, B., Gelosa., D., Kruglov, A., y Morbidelli, M., Kinetics of Liquid-Phase Esterification Catalyzed by Acidic Resins., Ind. Eng. Chem. Res., Vol 36, 1997, pp. 3-10. DOI: https://doi.org/10.1021/ie960450t
Orjuela, A., Leiva, F., Rodríguez, G., Boyacá, A., y Carballo, L., Estudio de la Síntesis de Acetato de Butilo 2. Análisis de las condiciones del equilibrio químico., Ingeniería e Investigación, Universidad Nacional de Colombia, Bogotá, Vol 25, No. 3, 2005, pp. 13-21.
Orjuela, A., Leiva, F., Rodríguez, G., Boyacá, A., y Carballo, L., Estudio de la Síntesis de Acetato de Butilo 3. Análisis de adsorción sobre el catalizador., Ingeniería e Investigación, Universidad Nacional de Colombia, Bogotá, Vol. 26, No. 1, 2006, pp. 15-24.
Orjuela, A., Evaluación de un Sistema de Destilación Reactiva a Nivel de Planta Piloto en Reacciones de Esterificación., Proyecto de Grado, Maestría en Ingeniería Química, Universidad Nacional de Colombia, Bogotá, 2003.
Orjuela, A., Leiva, F., Rodríguez, G., Boyacá, A., y Carballo, L., Estudio de la Síntesis de Acetato de Butilo 1. Selección del Catalizador., Ingeniería e Investigación, Universidad Nacional de Colombia, Bogotá, Vol. 24, 2004, pp. 50-60.
Peterson, M., y Way, J., Esterification., Ind. and Eng. Chem., Vol 48, 1956, pp. 1576-1584. DOI: https://doi.org/10.1021/ie51401a004
Saha, B., Chopade, S., y Mahajani, S., Recovery of dilute acetic acid through esterification in a reactive distillation column., Catalysis today, Vol 60, 1-2, 2000, pp. 147-157. DOI: https://doi.org/10.1016/S0920-5861(00)00326-6
Sánchez, F., y Rodríguez, G., Esterificación., Ingeniería e Investigación, Universidad Nacional de Colombia, Bogotá, Vol. 9, 1996, pp. 87-94. DOI: https://doi.org/10.15446/ing.investig.n33.20904
Smejkal, Q., y Soos, M., Comparison of computer simulation of reactive distillation using ASPEN PLUS and HYSYS software., Chem. Eng. and Proc., Vol 41, 2002, pp. 413-418. DOI: https://doi.org/10.1016/S0255-2701(01)00160-X
Song, W., Venimadhavan, G., Manning, J., Malone, M., y Doherty, M., Measurement of Residue Curve Maps and Heterogeneous Kinetics in Methyl Acetate Synthesis., Ind. Eng. Chem. Res., Vol 37, 1998, pp. 1917-1928. DOI: https://doi.org/10.1021/ie9708790
Steinigeweg, S., y Gmehling, J., n-Butyl Acetate Synthesis via Reactive Distillation: Thermodynamic Aspects, Reaction Kinetics, Pilot-Plant Experiments, and Simulation Studies., Ind. Eng. Chem. Res., 41, 2002, pp. 5483-5490. DOI: https://doi.org/10.1021/ie020179h
Teo, H., y Saha, B., Heterogeneous catalyed esterification of acetic acid with isoamyl alcohol: kinetic studies., Journal of Catalysis, 228, 2004, pp. 174 - 182. DOI: https://doi.org/10.1016/j.jcat.2004.08.018
Venimadhavan, G., Malone, M., y Doherty, M., A novel distillate policy for batch reactive distillation with application to the production of butyl acetate., Ind. Eng. Chem. Res., Vol 38, 1999, pp. 714-722. DOI: https://doi.org/10.1021/ie9804273
Wang, S., Wong, D., y Lee, E., Control of a Reactive Distillation Column in the Kinetic Regime for the Synthesis of n-butyl Acetate., Ind. Eng. Chem. Res., Vol 42, 2003, pp. 5182-5194. DOI: https://doi.org/10.1021/ie0209172
Wasylkiewicz, S., y Ung, S., Global phase stability analysis for heterogeneous reactive mixtures and calculation of reactive liquid-liquid and vapor-liquid-liquid equilibria., Fluid Phase Equilibria, 175, No. 1-2, 2000, pp. 253-272. DOI: https://doi.org/10.1016/S0378-3812(00)00451-9
Xu, Z., y Chuang, K., Kinetics of Acetic Acid Esterification over Ion Exchange Catalysts., The Canadian Jour. of Chem. Eng., Vol 74, 1996, pp. 493-500. DOI: https://doi.org/10.1002/cjce.5450740409
Yadav, G. D., y Kulkarni, H. B., Ion-Exchange Resin Catalysis in the Synthesis of Isopropyl Lactate., Reactive and Funct. Polymers, Vol 44, No.2, 2000, pp. 153 - 165. DOI: https://doi.org/10.1016/S1381-5148(99)00090-5
Yu, W., Hidajat, K., y Ray, A., Determination of adsorption and kinetic parameters for methyl acetate esterification and hydrolysis reaction catalyzed by Amberlyst 15., Applied Catalysis A: General, 260, 2004, pp. 191-205. DOI: https://doi.org/10.1016/j.apcata.2003.10.017
Zhicai, Y., Xianbao, C., y Jing, G., Esteritication-Distillation of Butanol and Acetic Acid., Chem. Eng. Sci., Vol 53, 1998, pp. 2081-2088. DOI: https://doi.org/10.1016/S0009-2509(98)00020-7
How to Cite
APA
ACM
ACS
ABNT
Chicago
Harvard
IEEE
MLA
Turabian
Vancouver
Download Citation
License
Copyright (c) 2006 Álvaro Orjuela Londoño, Fernando Leiva Lenis, Luis Alejandro Boyacá Mendivelso, Gerardo Rodríguez Niño, Luis María Carballo Suárez
This work is licensed under a Creative Commons Attribution 4.0 International License.
The authors or holders of the copyright for each article hereby confer exclusive, limited and free authorization on the Universidad Nacional de Colombia's journal Ingeniería e Investigación concerning the aforementioned article which, once it has been evaluated and approved, will be submitted for publication, in line with the following items:
1. The version which has been corrected according to the evaluators' suggestions will be remitted and it will be made clear whether the aforementioned article is an unedited document regarding which the rights to be authorized are held and total responsibility will be assumed by the authors for the content of the work being submitted to Ingeniería e Investigación, the Universidad Nacional de Colombia and third-parties;
2. The authorization conferred on the journal will come into force from the date on which it is included in the respective volume and issue of Ingeniería e Investigación in the Open Journal Systems and on the journal's main page (https://revistas.unal.edu.co/index.php/ingeinv), as well as in different databases and indices in which the publication is indexed;
3. The authors authorize the Universidad Nacional de Colombia's journal Ingeniería e Investigación to publish the document in whatever required format (printed, digital, electronic or whatsoever known or yet to be discovered form) and authorize Ingeniería e Investigación to include the work in any indices and/or search engines deemed necessary for promoting its diffusion;
4. The authors accept that such authorization is given free of charge and they, therefore, waive any right to receive remuneration from the publication, distribution, public communication and any use whatsoever referred to in the terms of this authorization.