A reaction network detailing the mechanistic origins of 17 C1−C7 byproducts in acrolein oxidation over a vanadium molybdate mixed oxide catalyst doped with antimony and copper is proposed based on measurements of acrolein oxidation rates with co-feeds of C1−C7 organics formed as byproducts, acrylic acid 13C isotopic tracer experiments, and probe molecule reactions. C1 and C2 products form via C−C bond scission of either the single or double C−C bond in acrolein and acrylic acid. C4−C7 products form by addition of one or two acrolein or acrylic acid molecules to a C2 surface species coupled with decarbonylation or decarboxylation events. Two-carbon ethyl and vinyl surface species and three-carbon acrolein-derived surface species are involved in all pathways that lead to byproduct formation; controlling the relative abundance and reactivity of such intermediates is integral to prescribing process conditions and material compositions for selective oxidation of acrolein.
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 Mr. Linh Bui, University of Minnesota, and Dr. Joseph DeWilde, The Dow Chemical Company, for valuable technical insights.
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- acrylic acid
- partial oxidation
- reaction pathways
- reducible oxide