Investigating the Impact of Incorporating Alkali Metal Cations on the Properties of ZSM-5 Zeolites in the Methanol Conversion into Hydrocarbons

Alkali metal-modified M-ZSM-5 zeolites (M: Li+, Na+, K+) were synthesized by cationic exchange and characterized using ICP-MS, XRD, N2 adsorption–desorption, Py-IR and NH3-TPD techniques to evaluate their elemental composition, structure, textural and acidic properties. In addition, XPS and DFT calculations were employed to study the effects of metal ion doping on the electronic structure and catalytic behavior. The latter catalytic performance was assessed in the methanol-to-olefin (MTO) reaction. The results showed that alkali metal doping facilitated the enhancement of the zeolite structural stability, adjustment of acid density, and increase in the adsorption energy of light olefins onto the active sites. During the reaction, olefin products shifted from Brønsted acid sites to alkali metal sites, effectively minimizing hydrogen transfer reactions. This change in the active site nature promoted the olefin cycle, resulting in higher yields in propylene and butylenes, reduced coke deposition, and prolonged catalyst lifetime. Among all zeolites, Li-exchanged ZSM-5 exhibited the best and extending the catalyst lifetime by 5 h.