Microkinetic Modeling of Lean NOx Trap Sulfation and Desulfation.

摘要

A microkinetic reaction sub-mechanism designed to account for the sulfation and desulfation of a commercial lean NOx trap (LNT) is presented. This set of reactions is appended to a previously developed mechanism for the normal storage and regeneration processes in an LNT in order to provide a comprehensive modeling tool. The reactions describing the storage, release, and reduction of sulfur oxides are patterned after those involving NOx, but the number of reactions is kept to the minimum necessary to give an adequate simulation of the experimental observations. Values for the kinetic constants are estimated by fitting semi-quantitatively the somewhat limited experimental data, using a transient plug flow reactor code to model the processes occurring in a single monolith channel. Rigorous thermodynamic constraints are imposed in order to ensure that the overall mechanism is consistent both internally and with the known properties of all gas-phase species. The final mechanism is shown to be capable of reproducing the principal aspects of sulfation/desulfation behavior, most notably (a) the essentially complete trapping of SO2 during normal cycling; (b) the preferential sulfation of NOx storage sites over oxygen storage sites and the consequent plug-like and diffuse sulfation profiles; (c) the degradation of NOx storage and reduction (NSR) capability with increasing sulfation level; and (d) the mix of H2S and SO2 evolved during desulfation by temperature-programmed reduction.