Ammoxidation of ethylene over low and over-exchanged Cr–ZSM-5 catalysts

Abstract

Catalytic performances of Cr–ZSM-5 catalysts (5 wt.% of Cr, Si/Al = 26), prepared by solid-state reaction and aqueous exchange, from Cr nitrate and Cr acetate precursors, were evaluated in the selective ammoxidation of ethylene into acetonitrile in the temperature range 425–500 °C. Catalysts were characterized by chemical and thermal analysis, XRD, N 2 physisorption, 27Al MAS NMR, TEM, UV–vis DRS, Raman, DRIFTS and H 2-TPR. Characterization results shown that solid-state exchange was favorable for Cr 2O 3 formation, while exchanging chromium in aqueous phase led, essentially, to Cr(VI) species. Catalysts were actives and selectives in the studied reaction, and among them, those, prepared from aqueous exchange, exhibited the highest acetonitrile yields (23 ± 0.5%, at 500 °C). Improved catalytic properties can be correlated with the chromium species nature. In fact, mono/di-chromates and/or polychromate species, sited in the charge compensation positions, were definitively shown, as being, the active sites. Furthermore, during solid-state reaction, the agglomeration of Cr 2O 3 oxide should be avoided since these species inhibit the catalyst activity.