Rutile-type Cr/Sb mixed oxides as heterogeneous catalysts for the ammoxidation of propane to acrylonitrile

Cr/Sb mixed oxides with a rutile-type structure were synthesized by calcining (700°C) a mixture of oxohydrates obtained by coprecipitation from an alcohol solution containing the required amount of the components. The samples were characterized using X-ray powder diffraction (XRD), FT-IR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). In the Cr/Sb/O compound prepared with Cr/Sb 1/0.8 (atomic ratio), an almost stoichiometric CrSbO₄develops (no antimony or chromium oxides are found), which however is characterized by enrichment in Sb in outmost rutile atomic layers, and thus by a non-homogeneous intracrystalline distribution of the two components. For Cr/Sb ratios lower than 1, the amount of Sb in the rutile-type structure exceeds the stoichiometric value. The reactivity of Cr/Sb/O catalysts with increasing Sb contents (from Cr/Sb 1/0.8 to 1/2.8) is slightly affected by the Cr/Sb atomic ratio. In particular, the selectivity increases with increasing Sb content, while the catalytic activity is higher for the samples having higher Cr/Sb ratios. The Cr/Sb/O system presents considerable differences with respect to the V/Sb/O rutile system; these differences are discussed in reference to the properties of the transition metal components of the rutile mixed oxides.