Abstract
► Toluene methylation was studied over HZSM-5, Mordenite/ZSM-5, and ZM13 (composite HZSM-5 and MCM-41). ► Alkylation ability of catalysts is; ZM13>HZSM-5>Mordenite/ZSM-5, disproportionation is reverse. ► Activation energies of methylation and disproportionation on HZSM-5 are the highest.
A kinetic study of toluene alkylation with methanol was performed over pure HZSM-5, mordenite/ZSM-5 (hybrid of mordenite and HZSM-5), and ZM13 (composite mixture of HZSM-5 and MCM-41 at pH 13). Experimental runs were conducted using a batch fluidized bed reactor at temperatures of 300, 350 and 400°C and reaction times of 3, 5, 7, 10, 13, 15 and 20s. The rate of toluene methylation and toluene disproportionation were studied on the three catalysts (toluene alkylation is usually accompanied by toluene disproportionation on acid catalyst). Based on the results obtained, a simplified power law kinetic model consisting of three reactions was developed to estimate the activation energies of toluene methylation and disproportionation simultaneously. Coke formation on catalysts was accounted for using both reaction time and reactant conversion decay functions. All parameters were estimated based on quasi-steady state approximation. Estimated kinetic parameters were in good agreement with experimental results. The order of alkylation ability of the catalysts was found to be ZM13>HZSM-5>mordenite/ZSM-5, while the reverse is for toluene disproportionation (mordenite/ZSM-5>HZSM-5>ZM13). Thus, alkylation of toluene is most favorable on ZM13 due to combined effect of mesoporosity induced through its synthetic route and acid content. Toluene/MeOH molar ratio of 1:1 was most suitable for toluene alkylation reaction.