Isomorphous Substitution in ZSM-5 in Tandem Methanol/Zeolite Catalysts for the Hydrogenation of CO2 to Aromatics.

Intensified reactors for conversion of CO2 to methanol (via hydrogenation) using metal oxide catalysts coupled with methanol conversion to aromatics in the presence of zeolites (e.g., H-ZSM-5) in a single step are investigated. Brønsted acid sites (BAS) in H-ZSM-5 are important sites in methanol aromatization reactions, and correlations of the reactivity with zeolite acid properties can guide reaction optimization. A classical way of tuning the acidity of zeolites is via the effect of the isomorphous substitution of the heteroatom in the framework. In this work, H-[Al/Ga/Fe]-ZSM-5 zeolites are synthesized with Si/T ratios = 80, 300, affecting the acid site strength as well as distribution of Brønsted and Lewis acid sites. On catalytic testing of the H-[Al/Ga/Fe]-ZSM-5/ZnO-ZrO2 samples for tandem CO2 hydrogenation and methanol conversion, the presence of weaker Brønsted acid sites improves the aromatics selectivity (CO2 to aromatics selectivity ranging from 13 to 47%); however, this effect of acid strength was not observed at low T atom content. Catalytic testing of H-[B]-ZSM-5/ZnO-ZrO2 provides no conversion of CO2 to hydrocarbons, showing that there is a minimum acid site strength needed for measurable aromatization reactivity. The H-[Fe]-ZSM-5-80/ZnO-ZrO2 catalyst shows the best catalytic activity with a CO2 conversion of ∼10% with a CO2 to aromatics selectivity of ∼51%. The catalyst is shown to provide stable activity and selectivity over more than 250 h on stream.