Effect of the chromium precursor nature on the physicochemical and catalytic properties of Cr–ZSM-5 catalysts: Application to the ammoxidation of ethylene

The catalytic performance of Cr–ZSM-5 catalysts prepared by solid-state reaction from different chromium salts (acetate, chloride, nitrate and ammonium dichromate) was evaluated in the selective ammoxidation of ethylene to produce acetonitrile. Cr–ZSM-5 catalyst characterization by chemical analysis, XRD, FTIR, N2 physisorption, 27Al MAS NMR, TEM/EDX, UV–visible DRS, XPS, Raman and DRIFT spectroscopies and H2-TPR is reported. From textural analysis, it is obvious, after chromium exchange, that a decrease of SBET and of porous volume is observed. On the other hand, FTIR, XRD and 27Al MAS NMR results show that there is no collapse of the parent zeolite during thermal treatment. From H2-TPR, DRS, Raman and XPS spectroscopies, it is concluded that Cr ions and Cr(III) oxide coexist. TEM/EDX results confirmed that chromium oxide species are either heterogeneously or homogeneously dispersed on the support, depending on the nature of the precursor. DRIFT showed that chromium exchange leads strictly to the consumption of Si–O+H–Al groups. The catalyst prepared from chromium chloride showed higher activity and selectivity towards acetonitrile, being this catalytic modification probably due to the differentiated nature of chromium species formed using this precursor. A similarity with Fe–ZSM-5 system is underlined. In fact, higher oxidation states of chromium species are required for ethylene ammoxidation, while Cr2O3 clusters seem to enhance the hydrocarbon oxidation.

Graphical abstractThe chromium precursor nature affects significantly the catalytic properties of Cr–ZSM-5 materials prepared by solid-state ion exchange. Catalytic behaviour depends on chromium speciation. In fact, high oxidation state of chromium species is requested in the ammoxidation of ethylene to acetonitrile while Cr2O3 clusters enhances the deep oxidation of hydrocarbon into CO2.Figure optionsDownload full-size imageDownload high-quality image (140 K)Download as PowerPoint slideHighlights► Cr–ZSM-5 solids were tested in the ammoxidation of ethylene to acetonitrile. ► There is no destruction of the parent zeolite during solid-state reaction. ► Cr(VI) ions and Cr(III) oxide species are predominant. ► Catalysts are active and selective towards acetonitrile. ► Cr(VI) species are requested in the ammoxidation, while Cr2O3 clusters are inadequate.