Ion-exchange resin catalyzed transesterification of ethyl acetate with methanol: Gel versus macroporous resins

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2014-04, Vol.242, p.170-179
• Main Authors: Van de Steene, Evelien, De Clercq, Jeriffa, Thybaut, Joris W.
• Format: Article
• Language: English
• Subjects: Catalytic activity; Cross-linking density; Ethyl acetate; Heterogeneous catalysis; Ion-exchange resin; Kinetics; Mathematical models; Methyl alcohol; Polymers; Reaction kinetics; Resins; Swelling; Transesterification
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2013.12.025

[Display omitted] •Resin swelling determines active site accessibility and, hence, catalytic activity.•Gel resins outperform macroporous ones in ethyl acetate transesterification with methanol.•The kinetic model implicitly accounts for swelling by assuming full active site coverage.•Protonated ethyl acetate reaction with bulk methanol is rate determining.•The selected Eley–Rideal mechanism is independent of the resin used. The liquid-phase transesterification kinetics of ethyl acetate with methanol to ethanol and methyl acetate catalyzed by gel (Lewatit K1221) and macroporous (Lewatit K2640, Lewatit K2629 and Amberlyst 15) ion-exchange resins have been investigated. The effects of the resins’ swelling, the initial reactant molar ratio (1:1–10:1) and the temperature (303.15–333.15K) on the reaction kinetics were assessed. Macroporous Lewatit K2629, Lewatit K2640 and Amberlyst 15 exhibit a clearly inferior catalytic activity compared to the gel type Lewatit K1221, despite the similar number of sulfonic acid active sites. This trend in catalytic activity can be explained by the differences in acid site accessibility, which are related to the resins’ swelling behavior and, hence, the extent of divinylbenzene cross-linking in the polymeric structure. A fundamental kinetic model, accounting for the chemical elementary steps as well as for the physical swelling due to solvent sorption, was constructed. According to this model (1) all active sites are initially occupied by protonated methanol, (2) the esters are activated by a proton exchange with protonated methanol and (3) the reaction occurs through an Eley–Rideal mechanism with the surface reaction of protonated ethyl acetate with methanol from the bulk as the rate-determining step. The kinetic model adequately described the experimental data as a function of temperature, initial molar ratio and catalyst resin type. A value of 49kJmol−1 was obtained for the activation energy, irrespective of the resin used. Differences in catalytic activity caused by the accessibility of the active sites are reflected by the values obtained for the reaction rate coefficient, which is 3–4-fold higher for a gel type resin compared to the macroporous ones.