Selective propene oxidation on mixed metal oxide catalysts

Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb2O5' and FeSbO4, and a significant difference between these and the Sb2O3 and Sb2O4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb5+. The lack of reactivity of Sb2O4 implies a similarity of the surface with that of Sb2O3, which is dominated by Sb3+. X-ray diffraction analysis of the 'Sb2O5' sample, together with computer modelling studies, have indicated that this sample is in fact an unusual morphology of the β-Sb2O4 phase. A comparison of the reactivity between iron antimonate (Fe:Sb = 1:2) and bismuth molybdate has revealed that the latter is more effective for the selective oxidation reaction due to its higher oxygen mobility and its ability to maintain a higher average surface oxidation state, due to oxygen vacancies being transported into the bulk material. A preliminary investigation into the effect of metal cation substitution within the bulk iron antimonate composition (Fe1-xAxSbO4, where A was cobalt or vanadium, and 0 ≤ x ≤ 1) showed that both the metal and its extent of substitution significantly affects the products formed during reaction. Low levels of cobalt or vanadium substitution (x = 0.2) enhance the selectivity towards acrolein, with the latter also providing a route for the direct conversion of acrolein into acrylic acid when operated within a fixed temperature regime. At high levels of substitution both metals increase the activity of the system and form undesired reaction products. A correlation between metal doping and product distributions has been proposed. Fundamental studies concerning the intermediate species involved during selective propene oxidation on iron antimonate have been carried out using inelastic neutron scattering. The identification of allyl species, by comparison of experimental spectra with those predicted from density functional theory calculations, suggests that the rate-determining step may not be the initial a-hydrogen abstraction to form the allyl, as is often assumed. (author)