Oxygen distribution in packed bed membrane reactors for partial oxidation systems and the effect on the product selectivity

Packed bed membrane reactors (PBMRs) are currently considered for the distributive addition of oxygen in partial oxidation systems. Among other advantages the decreased oxygen concentrations in the PBMR can result in improved product selectivities for reaction systems in which the oxygen dependency of the target product formation is less pronounced than that of the waste product formation. Oxidative dehydrogenation (ODH) of methanol to formaldehyde (Diakov et al., 2002) and ethylbenzene to styrene (Shakhnovich et al., 1984) are industrially relevant examples of such a kinetic system. To achieve considerable selectivity improvements the oxygen concentration should be kept small compared to hydrocarbon concentrations. However, a decrease of the oxygen concentration is accompanied with a decrease in the effectiveness of the catalyst particles since the intraparticle oxygen concentration gradients (and not the hydrocarbon concentration gradients) predominantly determine the actual activity and product selectivities of the catalyst, rendering the common effectiveness factors inapplicable for the modeling of a PBMR. Furthermore, concentration profiles over the radius of the packed bed can emerge, if the radial mass transport rate of oxygen from the membrane wall to the center of the bed is insufficient compared to the local oxygen consumption rate. If the transmembrane flux is dominated by convective transport as typical with porous membranes, the radial oxygen concentration profiles result in increased product losses, and the use of a one-dimensional reactor model may result in an overestimation of the product selectivity. In this paper the effect of limitations of the oxygen mass transport in a PBMR – i.e. intraparticle and from the membrane to the centerline of the packed bed – have been discussed for the ODH of methanol and ethylbenzene.