Cr/V/Sb mixed oxide catalysts for the ammoxidation of propane to acrylonitrile: Part I: Nature of the V species

Rutile-type Cr/V/Sb mixed oxides, catalysts for the ammoxidation of propane to acrylonitrile, were prepared and characterized. For atomic ratios between components equal to Cr/V/Sb 1/x/1 and 1/x/2 the systems were monophasic, but different types of compounds formed depending on the ratio between the three metals. The compositional parameter which most affected the nature of the compound formed was the (Cr+V)/Sb atomic ratio. When this ratio was between 2 and ≈1, a rutile Cr³⁺/V⁴⁺/Sb⁵⁺ mixed oxide of composition Cr₁V_xSb₁O_4+2x developed (0<x<1), which in practice corresponds to a solid solution between 1 CrSbO₄ and x VO₂. When the (Cr+V)/Sb ratio was between 0.5 and ≈1, a rutile Cr³⁺/V³⁺/Sb³⁺/Sb⁵⁺ mixed oxide of composition CrV_xSb_1+x+2zO_4+4x+4z developed (0<x<1), which corresponds to a solid solution between 1 Cr³⁺Sb_z³⁺Sb_1+z⁵⁺O_4+4z and x VSbO₄. The distinction between the two classes of compounds was not clear-cut, and when the (Cr+V)/Sb atomic ratio was around 1, mixed oxides containing both V³⁺ and V⁴⁺ formed. Values of the (Cr+V)/Sb atomic ratio lower than ≈0.5 led to the additional formation of antimony oxide.