Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics

•Crystal size of H-ZSM-5 is regulated by adding proper amount of silicalite-1 seeds.•Zn state and catalytic performance of Zn/H-ZSM-5 are related to the crystal size.•Overall acidity of H-ZSM-5 and Zn/H-ZSM-5 is less influenced by the crystal size.•Linear correlation lies between the amount of ZnOH+ and selectivity to aromatics.•Small crystal Zn/H-ZSM-5 with more ZnOH+ exhibits high selectivity to aromatics.

H-ZSM-5 zeolites with a uniform crystal size from 0.25 to 2 μm were obtained by adding colloidal silicalite-1 seed in the synthesis gel; with H-ZSM-5 as the support, Zn/H-ZSM-5 was prepared by incipient wet impregnation. The influence of crystal size on the state of Zn species and its relation to the catalytic performance of Zn/H-ZSM-5 in the conversion of methanol to aromatics (MTA) was then investigated. The results illustrated that the state of Zn species and catalytic performance of Zn/H-ZSM-5 are closely related to the crystal size, though the crystal size has little influence on the overall acidity. There exist mainly two types of zinc species, viz., ZnO and ZnOH+; Zn/H-ZSM-5 with smaller crystal size is provided with more ZnOH+ species. The selectivity to aromatics and catalyst stability can be improved greatly by using small crystal Zn/H-ZSM-5. A good linear correlation is observed between the amount of ZnOH+ species and the selectivity to aromatics, suggesting that ZnOH+ species plays an important role in enhancing the dehydrogenation of alkanes and aromatization of alkenes to aromatics. As a result, small crystal Zn/H-ZSM-5 with large portion of ZnOH+ species exhibits high selectivity to aromatics and long lifetime in MTA.

Graphic abstractThe state of Zn species and catalytic performance of Zn/H-ZSM-5 are closely related to the crystal size; small crystal Zn/H-ZSM-5 with large portion of ZnOH+ species exhibits high selectivity to aromatics in MTA.Download high-res image (291KB)Download full-size image