Chemical Engineering Science, Vol.195, 107-119, 2019
Kinetic study of the aqueous Kolbe-Schmitt synthesis of 2,4-and 2,6-dihydroxybenzoic acids
The Kolbe-Schmitt reaction is the traditional method for preparing 2,4- and 2,6-dihydroxybenzoic acid (2,4- and 2,6-DHBA). In this work, accurate kinetic models for the Kolbe-Schmitt synthesis of 2,4- and 2,6-DHBA were successfully developed. The relative errors between the theoretical and experimental 2,4-DHBA equilibrium yields are less than 3.7% as T = 348-473 K, [C6H6O2] = 0.4-0.8 M and [KHCO3] = 1.2-4.0 M. The effects of reaction temperature, reaction time, KHCO3 and resorcinol (C6H6O2) concentrations on the formation rates and the yields of 2,4- and 2,6-DHBA were investigated by the developed models. Results show that the 2,4-DHBA equilibrium yield exhibits a strong dependence on the KHCO3 concentration, and the formation rate of 2,4-DHBA is strongly dependent on the reaction temperature. Furthermore, the reaction time is a critical factor in controlling the ratio of 2,4-DHBA to 2,6-DHBA as the reaction temperature varies from 433 to 473 K. Additionally, the results of the present work deepen the understanding of the reaction mechanism, e.g. the rate-determining step and main reaction pathway of 2,6-DHBA formation. (C) 2018 Elsevier Ltd. All rights reserved.
Keywords:Kolbe-Schmitt reaction;2,4-Dihydroxybenzoic acid;2,6-Dihydroxybenzoic acid;Kinetic model;Activation energy;Rate-determining step