Recent developments in the selective oxidation of propane to acrylic and acetic acids

The oxidation of propane to acrylic and acetic acids has been studied using a Mo1Nb0.08Sb0.25V0.3 mixed oxide catalyst, calcined and activated before reaction under different conditions (T=500 or 600 °C in atmospheres of N2, static air, and flowing air (dry or with water or ammonia addition)). Catalytic testing was performed at 400 °C in a plug flow microreactor and the characterisation of the catalysts was carried out by XRD, XPS, BET, FT-IR and ammonia TPD. The best conditions for acrylic acid (AA) formation are calcination at 500 °C under N2, followed by activation at 500 °C prior to reaction under helium. The selectivity to acetic acid was found to be rather high, which was assigned to the presence of Sb instead of Te, which is used most often. The presence of all four elements, Mo, Nb, Sb and V, was found necessary to achieve high selectivities in acrylic and acetic acids. The presence of several crystalline phases, such as Sb4M10O31/Sb2M10O31 with M: Mo (major), Nb and/or V (minor), SbVO4, sub-oxides of MoO3, such as Mo8O23 and (MxMyMo1−x−y)5O14 with x and y referring to low amounts of V and Nb, and some amorphous phases, such as Sb2O4, was shown to be important in order to orientate the reaction toward the production of acrylic and/or acetic acids. The presence of MoO3 in all air-calcined samples was found to be detrimental to the selective oxidation of propane.