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

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, N2 physisorption, 27Al MAS NMR, TEM, UV–vis DRS, Raman, DRIFTS and H2-TPR. Characterization results shown that solid-state exchange was favorable for Cr2O3 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 Cr2O3 oxide should be avoided since these species inhibit the catalyst activity.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (148 K)Download as PowerPoint slideHighlights► Cr–ZSM-5 solids were tested in the ammoxidation of ethylene into acetonitrile. ► Cr(VI) ions and Cr(III) oxide species coexist. ► Solid-state exchange is favorable for Cr2O3 formation. ► Aqueous exchange catalysts showed better catalytic performances. ► Cr(VI) species are actives in the ammoxidation, while Cr2O3 oxide should be avoided.