Several Mars-Van Krevelen-type redox kinetic models were developed for the
catalytic oxidative dehydrogenation of propane and examined for their abili
ty to predict high propene yields at low oxygen/propane feed ratios. The in
tent in this study was to use modelling as a means of extracting further me
chanistic insight from experimental data rather than to identify the best m
odel. Thus, a conventional redox model with a consecutive reaction mechanis
m and a single pathway for the production of carbon oxides predicts higher
propene selectivity but only at the expense of low propane conversion. Expe
rimental data indicated, however, that even at the same propane conversion,
propene selectivity increased as the oxygen partial pressure was lowered.
Models that successfully describe the data had an additional carbon oxide p
roduction path involving the reaction of propane with deeply oxidizing surf
ace oxygen species. Kinetic models and experimental data examined do not fu
lly resolve how these deeply oxidizing surface oxygen species are formed. H
owever, they do reflect the accepted view that lattice oxygen selectively p
roduces propene whereas more weakly bound surface adsorbed oxygen reacts to
completely oxidize propane.