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Transient measurements of pre- and post-catalyst exhaust gas components and AFR are used to investigate the relationship between post-catalyst AFR and tailpipe emissions. This relationship is critical to the ability of on-board oxygen storage dominated models to predict emissions levels. The results suggest that under rich, or rich-biased conditions, dynamic deactivation processes significantly reduce catalyst efficiency, and that modeling oxygen storage effects alone may result in over-prediction of tailpipe pollutants. Catalyst deactivation is also shown to be correlated to hydrogen-induced distortion in the Exhaust Gas Oxygen (EGO) sensors used for measuring AFR. The dynamics of reversible catalyst deactivation are therefore important both for its direct effect on dynamic conversion efficiency, and for its indirect effect on dual EGO sensor dependent catalyst control and OBD strategies

The transient response of a catalytic converter to fluctuations in exhaust gas composition has a significant impact on tailpipe emissions. Advanced emission control strategies therefore need to incorporate a model for such behavior, which must also be sufficiently simple for practical implementation in-vehicle. To this end, a variety of semi-empirical models have been developed, including most recently a number of oxygen “storage-dominated” models. In this paper a new storage-dominated model is developed, which includes for the first time the effects of space velocity. The parameters of model may be estimated using the invariant embedding method.

The gas components CO, CO2, HC, NOx and the AFR in the exhaust from a SI engine, both upstream and down-stream of a Pd/Rh catalytic converter, have been monitored using fast response analyzers. Regular sequential step changes in the upstream air/fuel ratio (AFR), between two pre-set levels, have been implemented with both long and short periods between the steps. For transitions from rich to lean conditions, and vice-versa, several distinct zones for the output emissions characteristics, corresponding to different states of the catalyst surface, have been identified. These results suggest that, under reducing conditions, hydrogen is stored on the catalyst surface whereas under oxidizing conditions oxygen is stored by two different processes. These chemical insights facilitate the development of realistic models for tailpipe emissions from engines which are perturbed from steady state running.

The dynamic behavior of three-way catalysts has significant impact on tailpipe emissions levels, but remains one of the last unknowns in the overall vehicle emissions model. A simple empirical model (appropriate for use in real-time engine control and on-board diagnostic strategies) has therefore been identified using fast response input / output measurements of the actual process. The model is able to characterize the (significant) dynamic behavior which has recently been observed under rich conditions, as well as the more well known dynamics which arise from oxygen storage. The results therefore compare well with measured responses over a wide range of air / fuel ratio conditions.