Experimental study and kinetic modeling of methanol conversion to propylene with co-feeding of C4 and C5/C6 hydrocarbon cuts over a ZSM-5 catalyst

Abstract

Extensive experimental data were used to develop a comprehensive kinetic model for the methanol to propylene (MTP) process over a ZSM-5 catalyst. Preliminary experiments were performed to determine the reaction conditions that would ensure the absence of external (film) and internal mass transfer resistances. The kinetic experiments were subsequently carried out at 420–500 °C under conditions where mass transfer limitations were absent. A detailed reaction network was proposed for the MTP process based on the experimental product distribution and various reported kinetic models in the literature. According to the first series of experiments (without C4 and C5/C6 recycle streams) conducted at various temperatures, the best yield for propylene production was achieved at 480 °C with a water to methanol ratio of 0.7. Subsequently, kinetic experiments were performed at 480 °C and a water to methanol ratio of 0.7 using feeds with different amounts of C4 and C5/C6 hydrocarbons as recycle streams. Species material balances for the integral tubular reactor along with power-law rate functions and the Arrhenius equation for rate constants were employed in an optimization algorithm to obtain the kinetic parameters. The predictive ability of the model was checked against experimental data, and the kinetic parameters were validated by additional experiments.