Unravelling a complex catalyst deactivation in which selectivity affects conversion: oxygen-assisted styrene synthesis at industrially-relevant conditions

The oxidative dehydrogenation of ethylbenzene (EB) into styrene (ST) has been proposed as an alternative to the conventional energy-consuming synthesis of styrene. Various types of catalysts have been reported as promising for the reaction under industrially-relevant conditions. However, they show a complex deactivation behaviour. The EB conversion and the ST selectivity decay, with an increased CO_x selectivity. This phenomenon was investigated by means of experimental data and reaction model analysis, using two reference inorganic catalysts. The active catalyst is the deposited coke (ODH-coke) and not directly the inorganic material. The coke is formed in the initial reaction phase and promoted by the Lewis acid sites of the inorganic material. The reaction shows an activation period in which the ODH-coke is deposited and the EB conversion reaches a maximum where O₂ is fully converted. From that point onwards, the reaction model is applicable and the experimental data fit very well with low standard deviations. The model explains that the EB conversion′s decay with time on stream is associated to changes in the selectivity. Hence, EB conversion is not an independent parameter. This simplifies the understanding of this complex deactivation; the deactivating parameter is the selectivity. At this moment, we cannot discriminate between increased CO_x and decreased ST, or both effects, because both routes are competitive. This case represents a new type of catalyst deactivation behaviour, in which selectivity affects conversion.