Impact of mild hydrothermal aging on kinetics of NH[formula omitted], NO, SO[formula omitted] and CO oxidation reactions on Cu/SSZ-13 catalyst

Abstract

Cu/SSZ-13 is a catalyst commonly used for selective catalytic reduction (SCR) of nitrogen oxides (NOx) in diesel engine exhaust. Standard configurations are based on SCR preceded by an oxidation catalyst, however, a close-coupled SCR configuration appears relevant for upcoming regulations addressing cold-start emissions. Two often discussed ion-exchanged Cu sites in Cu/SSZ-13 are denoted ZCuOH and Z2Cu, where Z represents an Al atom in the zeolite framework. Mild hydrothermal aging (HTA) causes Cu redistribution within the catalyst; ZCuOH sites transform into more stable Z2Cu species. In this work, the effect of mild HTA on NH3, NO, SO2, and CO oxidation is studied on a commercial Cu/SSZ-13 sample. Temperature-programmed reaction experiments, performed in a lab reactor, and previously published catalyst characterization data using H2-TPR, NH3-TPD, and DRIFTS were used to build and validate a mathematical model. It couples the kinetics of the oxidation reactions with ZCuOH and Z2Cu concentration evolution during mild HTA. The model uses two distinct rate coefficients for ZCuOH and Z2Cu sites, allowing prediction of the catalyst activity during aging. The results suggest that the rate coefficients for the studied reactions on Z2Cu are effectively nil, so the observed activity in NH3, NO, SO2, and CO oxidation can be attributed solely to ZCuOH sites.