Deactivation kinetics of individual C6–C9 aromatics' generation from methanol over Zn and P co-modified HZSM-5

Abstract

A deactivation kinetic model has been determined for the methanol to aromatic process over a HZSM-5 zeolite catalyst (SiO₂/Al₂O₃ = 30) modified by 1.0 wt% ZnO and 2.0 wt% P, in which the generation rates of C₆–C₉ aromatics are treated individually while olefins and paraffins are lumped as intermediate and byproduct, respectively. The time-dependent catalytic activity is described by a deactivation coefficient related to the concentration of both methanol and products. The established kinetic model is able to predict the product distribution along with on-stream time under various conditions and is identified to be valid by a model significance test. The effect of operating conditions on catalyst behavior was also investigated: deactivation rate increases dramatically with methanol partial pressure and temperature; higher feed methanol content leads to less aromatics and more paraffin; increasing temperature reduces paraffin generation and results in higher aromatic yield, especially benzene and toluene.