Effects of Silicalite-1 Coating on the p-Xylene Selectivity and Catalytic Stability of HZSM-5 in Toluene Methylation with Methanol

The methanol-toluene alkylation process over zeolites catalysts offers a promising route for the production of p-xylene from low-cost feedstocks. Herein, we present a catalyst by preparing a core-shell aluminosilicate zeolite with an epitaxial silicalite-1 shell that passivates acid sites on the exterior surfaces. The para-selectivity was obviously increased due to the inhibition of the unselective isomerization of p-xylene over the external acid sites, and the open porous structure of the silicalite-1 shell ensured the mass transfer of reactants and products. Meanwhile, the carbon deposition was suppressed over HZSM-5@silicalite-1 catalysts, as a result of the decreased external acid sites. Furthermore, pulse chromatographic experiments revealed that the silicalite-1 coating could also improve the separation efficiency of p-xylene over o-xylene and m-xylene, due to the steric hindrance and extended diffusion path, resulting in a higher selectivity for p-xylene compared to that of the parent HZSM-5. The HZSM-5@4%S-1 catalyst showed the highest p-xylene selectivity (>80%) and methanol efficiency (66%), with good catalytic stability throughout the 170 h reaction time.