Comprehensive kinetic studies of the oxidation of methacrolein on mixed oxide (Mo, V, W) catalysts have been undertaken in order to find ways of catalyst improvement to achieve a high selectivity toward methacrylic acid. Steady-state kinetic experiments were carried out in a differential recycle reactor that behaves like an ideal continuous stirred tank reactor (CSTR). A kinetic model based on the scheme of Mars-van Krevelen was developed for a fair representation of the reaction rates of methacrolein conversion, methacrylic acid formation, byproduct formation, and selectivity toward methacrylic acid. For a better understanding of the kinetics, transient experiments were carried out in an apparatus to render possible sorption studies as well as transient kinetic experiments, which are powerful tools to study independently both the oxidation of the aldehydes on the catalyst in the absence of oxygen and the reoxidation of the catalyst. Steady-state kinetic data and transient experiments agree well. It could be clearly shown that the conversion of methacrolein is mainly determined by the reoxidation of the catalyst and that the selective oxidation of the aldehydes and the consecutive oxidation of the acids occur on different domains of the catalyst.
While the oxidation of acrolein on mixed oxide (Mo, V, W) catalysts shows an exceptionally high selectivity with respect to acrylic acid, the selectivity of the analogous oxidation of methacrolein is only moderate. This is due to a considerably lower oxidation rate of methacrolein compared to that of acrolein, while the undesired subsequent oxidation of methacrylic acid is of the same order of magnitude as the oxidation of acrylic acid. Comprehensive kinetic studies in particular by transient experiments have led to a sound hypothesis to explain this difference and to show ways of catalyst improvement for the conversion of methacrolein to methacrylic acid. A moderate increase of methacrylic acid selectivity could be reached by variation of the Mo/V ratio of the mixed oxide. Surprisingly the addition of phosphoric acid and Cs-acetate effected a reduction of the subsequent oxidation of methacrylic acid without affecting the methacrolein oxidation, leading to a marked increase of the selectivity toward methacrylic acid. Furthermore, the comparison of methacrolein and acrolein oxidation results in a confirmation of the hypothesis that aldehyde oxidation and subsequent oxidation of acid occur on different domains of the mixed oxide catalyst.
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