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A lean-rich hydrothermal aging was used to study the deactivation of Cu-zeolite SCR catalyst that has enhanced stability. Impact of DOC upstream on the SCR catalyst during the lean-rich aging was also investigated. The LR hydrothermal aging was conducted with the presence of hydrocarbon, CO and H₂ at different O₂ levels. It was found that the SCR catalyst was active for the oxidation of CO, H₂ and hydrocarbon, resulting in significant exotherm across the catalyst. In addition to hydrothermal aging, reductive aging, especially the presence of H₂ in the aging gas stream without O₂ presence during the L-R aging, might also contribute to the Cu/zeolite SCR catalyst deactivation. The impacts of DOC upstream on Cu/zeolite SCR catalysts depended on the aging temperatures. At lower aging temperature, the uncompleted oxidation of hydrocarbon and CO on the DOC might cause steam reforming and water-gas shift reactions on the DOC to form reductive gas stream.

A 2005 prototype diesel aftertreatment system consisting of diesel oxidation catalysts (DOC), Cu/zeolite Selective Catalytic Reduction (SCR) catalyst, and Catalyzed Diesel Particulate Filter (CDPF) was aged to an equivalent of 120k mi on an engine dynamometer using an aging cycle that incorporated both city and highway driving modes. The program demonstrated durable reduction in particulate matter (PM) and nitrogen oxides (NOx) emissions to federal Tier 2 levels on a 6000 lbs light-duty truck application. Very low sulfur diesel fuel (∼15 ppm) enabled lower PM emissions, reduced the fuel penalty associated with the emission control system, and improved long-term system durability. A total of 643 filter regenerations occurred during the aging that raised the entire catalyst system to high temperatures on a regular basis. After testing the aged system on a 6000 lbs light-duty diesel truck, a post mortem analysis was completed on core samples taken from the DOC, SCR catalyst, and filter.

Copper/zeolite catalysts are the leading urea SCR catalysts for NOx emission treatment in diesel applications. Sulfur poisoning directly impacts the overall SCR performance and is still a durability issue for Cu/zeolite SCR catalysts. Most studies on sulfur poisoning of Cu/zeolite SCR catalysts have been based on SO2 as the poisoning agent. It is important to investigate the relative poisoning effects of SO3, especially for systems with DOCs in front of Cu/zeolite SCR catalysts. It was observed that SCR activity was significantly reduced for samples poisoned by SO3 vs. those poisoned by SO2. The sulfur was released mainly as SO2 for both samples poisoned by SO2 and SO3. The temperatures and the magnitudes of released SO2 peaks however, were very different between the samples poisoned by SO2 vs. SO3. The results indicate that sulfur poisoning by SO2 and SO3 are not equivalent, with different poisoning mechanisms and impacts.

Base metal/zeolite catalysts, particularly containing copper and iron, are among the leading candidates for treatment of NOx emissions for diesel applications. Even with the use of ultra low sulfur fuel, sulfur poisoning is still a durability issue for base metal/zeolite SCR catalysts. In this study, the impact of sulfur poisoning on SCR activity and the stored sulfur removal effectiveness were investigated on several Cu and Fe/zeolite SCR catalysts after different thermal aging. The impact of sulfur was more significant on the Cu than on Fe/zeolite SCR catalysts for the NOx activity. It was found that the sensitivity of thermal aging status to the sulfur poisoning impact was different. The impact of sulfur on NOx activity changed with thermal aging on some catalysts, while it remained relatively the same for other catalysts. The most thermally durable SCR catalyst was not necessarily the most durable to sulfur poisoning.

Temperature programmed reduction by CO, H2, and propylene (C3H6), as well as hydrothermal aging in the presence of mixture of NO, HC, CO, H2 and O2 were used to study the deactivation of Cu/zeolite SCR catalysts. The presence of CO had no detrimental effect on catalyst activity. Carbonaceous deposit on the catalyst surface from propylene (C3H6) reduction suppressed the catalyst activity and burn off of carbonaceous deposit recovered activity, the presence of O2 suppressed carbonaceous deposit formation. The presence of H2 under lean conditions had much less effect on catalyst activity than H2 presence under rich conditions. Rich conditions with O2 presence represented the most detrimental effect on catalyst activity.

Selective Catalytic Reduction (SCR) of NOx with aqueous urea and a Catalyzed Diesel Particulate Filter (CDPF) has been considered as one of the emission control systems for diesel vehicles required to meet Federal Tier 2 and California LEVII emission standards. At Ford Motor Company, a DOC-SCR-CDPF system containing a copper / zeolite SCR catalyst was aged to 120k mi on the engine dynamometer using an aging cycle that mimicked both city and highway driving modes. A total of 643 CDPF regenerations occurred during the aging that raised the SCR catalyst to a temperature of up to 650°C on a regular basis. A series of lab analyses including activity tests, ammonia thermal desorption, BET surface area, XRF, XRD, and EPMA was conducted on cores taken from the 120k mi engine aged SCR catalyst brick. The lab post-mortem characterizations revealed the changes of catalyst properties, and the deterioration profile of the SCR catalyst brick after undergoing real aging conditions.

This paper presents a study of urea SCR catalyst aging characteristics and implementation into an analytical model that complements laboratory based experiments for a dynamometer-aged SCR brick. The model calibration is based on measured data taken from a 120k-mile simulated dynamometer-aged base metal/zeolite SCR. Dynamometer aging led to non-uniform axial deterioration with more severe deactivation toward the front of the SCR brick compared to the rear. Data from a 120k-mile simulated hydrothermally oven-aged SCR (uniform axial aging) is used to establish baseline aged NOx performance and NH3 adsorption/desorption behavior. An axial deterioration factor is applied to the baseline model to account for differences between oven and dynamometer aging. The model is exercised using engine out vehicle data to examine how different aging processes (oven vs. dynamometer) affect overall NOx performance during the EPA FTP (Environmental Protection Agency Federal Test Procedure).

Urea-based Selective Catalytic Reduction (SCR) has the potential to meet U.S. Diesel Tier 2 Bin 5 emission standards for NOx in 2010. The operating and driving conditions of light-duty and heavy-duty vehicles make it necessary to customize catalyst features to the application. This paper reviews the selection of SCR catalyst technology for the U.S. and the appropriate aging and poisoning protocols for current supplier SCR catalysts. Generally, light-duty applications require SCR catalysts to function well at low temperature whereas heavy-duty applications require functionality at high temperature and high space velocity. One main durability requirement of SCR formulations involves withstanding the high temperature process of regenerating particulate filters from accumulated soot. Unrefined engine exhaust temperature control coupled with the inexact temperature measurement may also expose SCR catalysts to additional over-temperature conditions.

An analytical model was developed to simulate both sulfur adsorption and desorption characteristics based on the laboratory determined parameters. Diesel Lean NOx Trap (LNT) was tested under laboratory conditions to examine desulfation (deSOx) characteristics. Effects of different Lean/Rich (L/R) cycling of Air-Fuel ratio during the deSOx mode were investigated. The gradient of adsorbed sulfur along the axial direction of the sample LNT was also examined. The gradient of sulfur deposit, together with different L/R cycling combinations for the deSOx mode was critical to develop the efficient sulfur removal strategies. The model considered energy and mass balances during sulfur adsorption and desorption modes to predict the catalyst temperature and the amount of sulfur adsorbed and removed. HC and CO oxidation reactions as well as the oxygen storage were considered to estimate heat generated by the exothermic reactions.

Promising lean NOx trap (LNT) results on lean-burn gasoline engines have encouraged the development of LNTs for diesel applications. Although the fundamentals of LNT are common for both gasoline and diesel applications, there are major differences due to the character of engine operation and control strategies. The sulfur tolerance and thermal durability of current state-of-the-art diesel LNTs under the conditions that represent the thermal and chemical conditions in diesel exhaust were investigated in a laboratory flow reactor. Sulfur poisoning and thermal aging are unavoidable factors contributing to diesel LNT deactivation. The results show that sensitivity to sulfur poisoning varies with the catalyst formulations, and in some formulations the sulfur poisoning appears reversible. However, the thermal deactivation is permanent regardless of its cause, i.e., LNT de-sulfation (deSOx) or diesel particular filter (DPF) regeneration.