Influence of the parent zeolite structure on chromium speciation and catalytic properties of Cr-zeolite catalysts in the ethylene ammoxidation

Cr-zeolites with MFI, BEA, MOR and FAU structures, prepared by solid-state ion exchange, were characterized and tested in C2H4 ammoxidation to acetonitrile in the temperature range 425–500 °C. Based on characterization results, chromate and/or polychromate species, oxo-cations and small Cr2O3 oxide clusters played a key role in the ammoxidation of ethylene, while agglomerated Cr2O3 and bare Cr cations should be avoided. Cr ions sited in the sodalite and hexagonal cages of NH4+–Y are not accessible to the reactants while available catalytic sites are poorly active. However, the mesopores of the ultra stable Y zeolite (USY) favor the diffusion of reactants to the clustered Cr oxide. The corresponding catalyst is therefore active, but the presence of octahedral Al species is crucial to the ammoxidation. Cr ions in zeolites beta and mordenite led to less active catalysts when compared to ZSM-5. In zeolite beta, the micropores are small; therefore, pronounced interactions between ethylamine intermediate molecules could discourage the acetonitrile formation. In mordenite, agglomerates of Cr2O3 oxide inhibited the accessibility of active sites to the reactants and enhanced the hydrocarbon oxidation. The catalytic performance of Cr ions in ZSM-5 provided from a synergy of different parameters: structural, textural and the acid strength (Si/Al ratio).

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► Cr–S solids (S = ZSM-5, mordenite, beta, USY, Y) were tested in C2H4 ammoxidation.
► Cr species with high oxidation states play a key role in the ammoxidation.
► Agglomerated Cr2O3 and bare Cr ions should be avoided during catalyst preparation.
► Catalytic activity is highly affected by the zeolite matrix.
► Interactions between ethylamine intermediate molecules inhibit CH3CN formation.