Deactivation Kinetics of the Catalytic Alkylation Reaction

Abstract

A kinetics theory of catalyst deactivation is presented of the solid acid-catalyzed alkylation reaction of isobutane with propylene or butene that gives alkylate, a high octane fuel, as product. The intimate relation between the kinetics network of the reaction, catalyst deactivation kinetics, and residence time distribution is analyzed. The question is addressed why the deactivation of the alkylation reaction in a continuously stirred tank reactor (CSTR) is slow compared to that in a tubular plug flow reactor (PFR). Conditions are derived where such differences will be minimum and maximum. In the reaction regime of high alkylate selectivity, linear and quadratic power law kinetics equations in propylene concentration can be deduced from microkinetics. They are used to derive analytical expressions of deactivation times for CSTR and PFR. The theoretical power law kinetics equations can be related to previously established empirical rate equations of catalyst deactivation. We show that, in the CSTR, the self-alkylation reaction path contributes substantially to the deactivation time. In the self-alkylation reaction, alkylate is formed by reaction of the isobutene reaction intermediate and isobutane. Catalysts of high proton strength can benefit catalyst deactivation times by suppressing the carbenium ion deprotonation reaction that produces alkenes as isobutene. In the PFR, selective alkylate formation occurs only when the reaction occurs in a reaction zone of the catalyst bed. Deactivation is faster than in CSTR because of the reactant profile in the reaction zone. This reaction zone has restricted mobility due to the fast deactivation of reactive protons located behind the reaction zone by alkenes formed by nonselective reactions in the reaction zone. In PFR, as long as the reaction is limited to an immobile reaction zone, deactivation time is independent of reaction site density and contact time. Contact time dependence arises when the reaction zone is mobile. Overall deactivation time then depends strongly on the degree of deactivation of the protons behind the reaction zone.