Kinetics of esterification of propionic acid with n-amyl alcohol in the presence of cation exchange resins

Catalysis Reaction Engineering, Industrial Chemistry

Abstract

Esterifications of n-amyl alcohol with propionic acid catalyzed by macroporous (Amberlyst-15) and microporous (Dowex 50 W and Amberlite IR-120) polymeric ion-exchange resins were carried out between 333–348 K. When these catalysts were used as commercially available, Amberlyst-15 was observed to be the most effective catalyst with respect to rate constants, but after drying it became the less effective one. The reaction rate increased with increase in catalyst concentration and reaction temperature. Stirrer speed and different mesh sizes had virtually no effect on the rate under the experimental conditions. The effect of divinylbenzene content was examined for the microporous resin Dowex 50W, and the results showed that the propionic acid conversion decreased as the divinylbenzene content was increased. The rate data were correlated with a second-order homogeneous reaction model. The apparent activation energies, reaction enthalpies and entropy values were calculated for each catalyst. Reaction monitoring is simple and fast by volumetric method and the reproducibility of this method was the order of ± %2.54.

Key words

Esterification Ion-exchange Resin Heterogeneous Catalysis Kinetics Propionic Acid n-Amyl Alcohol 

References

  1. Chakrabarti, A. and Sharma, M.M., “Cationic ion exchange resins as catalyst,” Reactive Polymers, 20, 4 (1993).CrossRefGoogle Scholar
  2. Coutinho, F.M.B., Souza, R.R. and Gomes, A. S., “Synthesis, characterization and evaluation of sulfonic resins as catalysts,” European Polymer Journal, 40, 1531 (2004).CrossRefGoogle Scholar
  3. Gerasimov, Ya., Dreving, V. and Eremin, E., Physical chemistry, Volume: 1, MIR Publishers, Moscow, 507 (1974).Google Scholar
  4. Hart, M., Fuller, G., Brown, D. R., Dale, J.A. and Plant, S., “Sulfonated poly(styrene-co-divinylbenzene) ion-exchange resins: acidities and catalytic activities in aqueous reactions,” Journal of Molecular Catalysis A: Chemical, 182–183, 445 (2002).Google Scholar
  5. Hause, J. E., Principles of chemical kinetics, Wm.C. Brown Publishers, USA, 61 (1997).Google Scholar
  6. Kırbaşlar, Ş. I., Baykal, Z. B. and Dramur, U., “Esterification of acetic acid with ethanol catalysed by an acidic ion-exchange resin,” Turk J. Engin. Environ. Science, 25, 570 (2001).Google Scholar
  7. Kırbaşlar, Ş. I., Terzioğlu, H. and Dramur, U., “Catalytic esterification of methyl alcohol with acetic acid,” Chinese Journal of Chem. Engineering, 9, 93 (2001).Google Scholar
  8. Levenspiel, O., Chemical reaction engineering, John Wiley & Sons, Inc., Canada, 63 (1972).Google Scholar
  9. Lilja, J., Aumo, J., Salmi, T., Murzin, D.Yu., Maki-Arvela, P., Sundell, M., Ekman, K., Peltonen, R. and Vainio, H., “Kinetics of esterification of propanoic acid with methanol over a fibrous polymer-supported sulphonic acid catalyst,” Applied Catalysis A: General, 228, 255 (2002).CrossRefGoogle Scholar
  10. Lilja, J., Murzin, D.Yu., Salmi, T., Aumo, J., Maki-Arvela, P. and Sundell, M., “Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the Taft equation,” Journal of Molecular Catalysis A: Chemical, 182–183, 556 (2002).Google Scholar
  11. Liu, W. T. and Tan, C. S., “Liquid-phase esterification of propionic acid with n-butanol,” Ind. Eng. Chem. Research, 40, 3281 (2001).CrossRefGoogle Scholar
  12. Mahajani, S.M., “Reactions of glyoxylic acid with aliphatic alcohols using cationic exchange resins as catalysts,” Reactive & Functional Polymers, 43, 254 (2000).CrossRefGoogle Scholar
  13. Park, S.W., Cho, H. B., Suh, D. S. and Kim, C.W., “Esterification of lauric acid with isopropyl alcohol by tricaprylylmethylammonium chloride as a catalyst in a liquid-liquid heterogeneous systems,” Korean J. Chem. Eng., 16, 221 (1999).CrossRefGoogle Scholar
  14. Rodriguez, O. and Setinek, K., “Dependence of esterification rates on crosslinking of ion exchange resins used as solid catalysts,” Journal of Catal., 39, 449 (1975).CrossRefGoogle Scholar
  15. Roy, R. and Bhatia, S., “Kinetics of esterification of benzyl alcohol with acetic acid catalysed by cation-exchange resin,” Journal of Chem. Technology Biotechnol., 37, 6 (1987).Google Scholar
  16. Weissermel, K. and Arpe, H. J., Industrial organic chemistry, 2nd revised and extended edition, VCH Publishers Inc., New York, 289 (1993).Google Scholar
  17. Xu, Z. P. and Chuang, K. T., “Kinetics of acetic acid esterification over ion exchange catalysts,” The Canadian Journal of Chemical Engineering, 74, 494 (1996).CrossRefGoogle Scholar
  18. Yadav, G. D. and Bhagat, R. D., “Experimental and theoretical analysis of Friedel-Crafts acylation of thioanisol to 4-(methythio) actophenone using solid acids,” Journal of Molecular Catalysis A: Chemical, 235, 101 (2005).CrossRefGoogle Scholar
  19. Yadav, G. D. and Kulkarni, H. B., “Ion-exchange resin catalysis in the synthesis of isopropyl lactate,” Reactive & Functional Polymers, 44, 164 (2000).CrossRefGoogle Scholar
  20. Yadav, G. D. and Mehta, P. H., “Heterogeneous catalysis in esterification reactions: preparation of phenethyl acetate and cyclohexyl acetate by using a variety of solid acidic catalysts,” Industrial Eng. Chem. Research, 33, 2198 (1994).CrossRefGoogle Scholar

Copyright information

© Korean Institute of Chemical Engineering (KIChE) 2006

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Science and ArtsUludag UniversityBursaTurkey

Personalised recommendations