Evolution of the pore and framework structure of NaY zeolite during alkali treatment and its effect on methanol oxidative carbonylation over a CuY catalyst

Abstract

Alkali treatment is widely used on aluminosilicate zeolites with high Si/Al ratios in order to fabricate mesopores in the framework. However, for zeolites with low Si/Al ratios, the effect of alkali treatment on the pore and framework structure needed further study. In this work, Y zeolite is treated with NaOH solutions of different concentrations and is used as the support for Cu-based catalysts for oxidative carbonylation of methanol to dimethyl carbonate. The physicochemical properties of the supports and corresponding catalysts are characterized by N2adsorption–desorption, X-ray diffraction, X-ray fluorescence, transmission electron microscopy, inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, and H2-temperature-programmed reduction analyses. The results show that no obvious mesopores are formed under alkali treatment, even at high NaOH concentration. However, amorphous species present in the micropores of Y zeolite are removed, which increases the micropore surface area as well as the crystallinity. Simultaneously, the cage structure is partially destroyed, which also leads to a slight increase of the pore volume and surface area. The altered micropore structure eventually increases the content and accessibility of the exchanged Cu species, which is beneficial to the catalytic activity. When the concentration of NaOH is 0.6 M, the space time yield of dimethyl carbonate for the corresponding catalyst was 151.4 mg g−1 h−1which is 3.3-fold higher than that of the untreated-Y-zeolite-supported Cu catalyst. However, further increasing the alkali treatment strength can seriously destroy the basic aluminosilicate structure of the Y zeolite and decrease its intrinsic ion-exchange capacity. This results in the formation of agglomerated CuO on the catalyst surface, which was not conducive to catalytic activity.