Kinetic Modeling of Acrolein Oxidation Over a Promoted Mo−V Oxide Catalyst

A kinetic model describing the synthesis of 17 C₁−C₇ products observed during oxidation of acrolein at 498 K over a promoted MoVO_x catalyst is presented. Routes for C₁ and C₂ species production by C−C scission of acrolein and acrylic acid and C₄₊ product generation by C−C bond formation, which involve reactions between either a vinyl or methyl surface species and either acrolein or acrylic acid, are discussed. The model accurately describes transient evolution of acrolein, O₂, water, and 17 products in 33 independent batch reaction experiments. Forward simulation of the model matches experimental observation of instantaneous ¹³C content across byproducts during a co-feed of ¹³C₃ acrylic acid, validating pathway and parameter accuracy. Estimation of surface coverages reveals comparable fractions of lattice oxygen and vacancy sites at all measured PO₂ and P_C3H4O. Comparison of model parameters governing production of CO and CO₂ shows that the two combustion products arise primarily from acrolein, with smaller contributions from acrylic acid, while comparison of rate and equilibrium parameters governing production of all other side products reveals that acrolein and acrylic acid play comparable roles in formation of these species.