A kinetic model describing the synthesis of 17 C1−C7 products observed during oxidation of acrolein at 498 K over a promoted MoVOx 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 PC3H4O. 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.
Bibliographical noteFunding Information:
The authors acknowledge financial support from The Dow Chemical Company as well as a departmental fellowship sponsored by 3M. The authors also acknowledge Dr. Joseph DeWilde, The Dow Chemical Company, and Mr. Linh Bui, University of Minnesota, for valuable technical insights.
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- kinetic modeling
- partial oxidation
- reaction pathways
- reducible oxide