Selectivity engineering in isopropylation of mesitylene with isopropyl alcohol over cesium substituted heteropolyacid supported on K-10 clay

Abstract

Alkylation of aromatics catalyzed by solid acids constitutes a class of reactions of both academic and industrial importance. Among alkylation reactions, isopropylation of aromatic compounds has attracted considerable attention. Use of propylene as alkylating agent at very high temperatures leads to coke formation which results in deactivation of the catalyst. The use of isopropanol (IPA) as an alkylating agent is attractive when propylene is not readily available. In situ dehydration of IPA leads to prolonged activity since water of reaction suppresses coke formation. Further, IPA dehydration also generates diisopropyl ether which itself is an excellent alkylating agent. Alkylation of mesitylene with propylene or IPA results in the formation of 2-isopropyl-mesitylene (2-IPMT), which is almost extensively used as a precursor in a number of industrial chemicals. This work covers the evaluation of clay-supported heteropolyacids and sulfated zirconia. A variety of solid acid catalysts such as K-10 clay, sulfated zirconia, Filtrol-24, 20% w/w dodecatungstophosphoric acid (H3PW12O40, DTP) supported on K-10 montmorillonite clay and 20% w/w cesium substituted dodecatungstophosphoric acid (Cs2.5H0.5PW12O40, Cs-DTP) supported on K-10 montmorillonite clay were investigated for the liquid phase isopropylation of mesitylene to 2-IPMT using IPA at much milder conditions vis-à-vis other catalysts reported so far. 20% w/w Cs-DTP/K-10 clay was found to be the best catalyst which gives 98% conversion of limiting component, IPA and 98% selectivity towards the desired product, 2-IPMT after 2 h of total reaction time. This catalyst could be reused without any further chemical treatment, eliminating the effluent disposal problems. The reaction was carried out without using any solvent and the process subscribes to the principles of green chemistry. The catalytic activity is in the following order: 20% w/w Cs-DTP/K-10 clay (most active) > 20% w/w DTP/K-10 clay > Filtrol-24 > Sulfated zirconia > K-10 clay (least active). The effect of various operating parameters and catalyst reusability were also systematically investigated. A mathematical model was proposed to probe into the intricate reaction kinetics and mechanism consistent with the experimental results. The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. An overall second order kinetic equation was used to fit the experimental data, under the assumption that all the species are weakly adsorbed on the catalytic sites.