Palladium–silver sol–gel catalysts for selective hydrodechlorination of 1,2-dichloroethane into ethylene: IV. Deactivation mechanism and regeneration

The activity and selectivity of a 1.9% Pd–3.7% Ag/SiO2 catalyst during selective hydrodechlorination of 1,2-dichloroethane into ethylene have been followed in the course of time. The deactivation curves show two distinct periods: an initial period at the very beginning of catalyst operation, that is, during the first 20 operating hours, characterized by a sharp decrease of the rates of both reactions involved in the process (1,2-dichloroethane hydrodechlorination and undesired ethylene hydrogenation) and a second period, after the first 20 operating hours and investigated for more than 600 h, characterized by a clearly slower deactivation. During the initial period, the hydrodechlorination rate decreases less quickly than the hydrogenation rate and this results in a fast increase of ethylene selectivity which reaches a maximum at the end of this period. After the initial period, the hydrodechlorination rate decreases faster than the hydrogenation rate and this results in a slow decrease of ethylene selectivity. A comparison between the physico-chemical properties of the fresh catalyst and of the deactivated one suggests a deactivation mechanism by poisoning or coking of silver sites at the surface of the active Pd–Ag alloy particles whereas palladium sites would remain intact. The selectivity evolution during the second period, that is, after the very first operating hours, is in agreement with such a mechanism. However, the sharp ethylene selectivity increase during the initial operating hours suggests, in addition to the deactivation by silver sites disappearance, the presence of a further nonidentified phenomenon. The characterization of the catalyst after a regeneration treatment including an oxidation step followed by a reduction step shows that this treatment allows restoration near to the physico-chemical properties of the fresh catalyst.