Abstract
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•Zn species exchange protons of HZSM-5 zeolite decreasing Brønsted acid sites.•P species interact with Al framework causing its dealumination and loss of silanols.•Zn slows down methanol transformation but above all, the deactivation.•Zn has a greater effect on slowing the formation of intermediates and coke species.•Zn increases the propylene-to-ethylene ratio.
The benefits of H-ZSM-5 zeolite modification with H3PO4 or ZnCl2 have been analyzed during the methanol to olefins (MTO) reaction. The catalysts were prepared, characterized and tested using three different reactors: fixed-bed, operando FTIR and UV–vis. The spent catalysts were further characterized for analyzing the nature and location of the species trapped. The results show that the zeolite modified with H3PO4 has suffered a simultaneous dealumination, leading to a decrease of number of acid sites and activity. However, the zeolite modified with ZnCl2 shows the inclusion of Zn transforming Brønsted into Lewis acid sites, leading to reaction intermediates (hydrocarbon pool species) that decreases the rate of reaction but improves propylene selectivity (+10%), slows downs coke formation (-42%) and expands catalytic lifetime (+80%). The distinct effect of Zn modification, typically associated with the promotion of aromatics, is explained on the grounds of the severe transformation of the strong and Brønsted acid sites.