Date Available

2-7-2013

Year of Publication

2013

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Engineering

Department/School/Program

Chemical and Materials Engineering

First Advisor

Dr. Stephen Rankin

Second Advisor

Dr. Mark Crocker

Abstract

THE EFFECTS OF CERIA ADDITION ON AGING AND SULFATION OF LEAN NOx TRAPS FOR STAND ALONE AND LNT-SCR APPLICATIONS

Model powder and fully formulated monolithic lean NOx trap (LNT) catalysts were used to investigate the effect of ceria on desulfation behavior. Temperature-programmed reduction (TPR) experiments (model catalysts) showed each of the oxide phases present is able to store sulfur and possesses distinct behavior (temperature at which desulfation occurs). La-CeO2 or CeO2-ZrO2-containing samples (monoliths) showed a greater resistance to deactivation during sulfation and required lower temperatures to restore the NOx storage efficiency to its pre-sulfation value.

Fully formulated monolithic LNT catalysts containing varying amounts of Pt, Rh and BaO were subjected to accelerated aging to elucidate the effect of washcoat composition on LNT aging. Elemental analysis revealed that residual sulfur, associated with the Ba phase, decreased catalyst NOx storage capacity and that sintering of the precious metals resulted in decreased contact between the Pt and Ba phases.

Spatially-resolved inlet capillary mass spectrometry (SpaciMS) was employed to understand the factors influencing the selectivity of NOx reduction in LNT catalysts degreened and thermally aged) containing Pt, Rh, BaO and Al2O3, and contained La-stabilized CeO2. Stretching of the NOx storage and reduction zone (NSR) zone resulted in increased selectivity to NH3 due to the fact that less catalyst was available to consume NH3 by either the NH3-NOx SCR reaction or the NH3-O2 reaction. Additionally, the loss of oxygen storage capacity (OSC) and NOx storage sites, along with the decreased rate of NOx diffusion to Pt/Rh sites, led to an increase in the rate of propagation of the reductant front after aging, in turn, resulting in increased H2:NOx ratios at the Pt/Rh sites and consequently increased selectivity to NH3.

Finally, a crystallite scale model was used to predict selectivity to NH3 from the LNT catalysts during rich conditions after a fixed amount of NOx was stored during lean conditions. Both the experimental and model predicted data showed that the production of NH3 is limited by the rate of diffusion from the Ba storage sites to the Pt particles at 200 °C. At 300 °C, the process is limited by the rate at which H2 is fed to the reactor.

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