Search Results

Despite drastic reduction of sulfur content in diesel fuel in the recent years, especially with the introduction of Ultra-Low Sulfur Diesel (ULSD), sulfur poisoning remains one of the most significant factors impacting performance of various catalysts in diesel aftertreatment systems. This is because even with ULSD, cumulative exposure of a catalyst over its lifetime in a heavy-duty diesel system may amount to kilograms of sulfur. In this study, we have found that the impact of sulfur poisoning on the performance of various diesel oxidation catalysts (DOC) strongly depends on the catalyst's operation history. For example, exposing a DOC to limited amounts of freshly deposited sulfur in bench reactor testing was shown to have a substantial detrimental effect. On the other hand, several samples which returned from vehicle or test-cell aging with high sulfur loading, have shown no signs of poisoning.

Stoichiometric natural gas engines with three-way catalysts emit less NOx and CH4 due to their higher efficiency compared to lean-burn natural gas engines. Although hydrothermal aging of three-way catalysts has been extensively studied, a deeper understanding beyond hydrothermal aging is needed to explain real-world performance, especially for natural gas engines with near-zero NOx emissions. In this investigation, field-aged three-way catalysts were characterized to identify the contribution of chemical aging to their overall performance. It was found that the sulfur species on the field-aged TWCs were entirely distributed along the catalyst length, showing a decreasing trend, whereas phosphorous contamination was mainly observed at the inlet section of the three-way catalysts, and the phosphorous concentration declined sharply along the axial length.

An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.

Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.

The ammonia slip catalyst (ASC), typically composed of Pt oxidation catalyst overlaid with SCR catalyst, is employed for the mitigation of NH3 slip originating from SCR catalysts. Oxidation and SCR functionalities in an ASC can degrade through two key mechanisms i) irreversible degradation due to thermal aging and ii) reversible degradation caused by sulfur-oxides. The impact of thermal aging is well understood and it mainly degrades the SCR function of the ASC and increases the NH3 conversion to undesired products [1]. This paper describes the impact of sulfur-oxides on critical functions of ASC and on NH3 oxidation activity and selectivity towards N2, NOx and N2O. Furthermore impact of desulfation under selected conditions and its extent of ASC performance recovery is explained.

The high global warming potential of nitrous oxide (N2O) led to its inclusion in the list of regulated greenhouse gas (GHG) pollutants [1, 2]. The mitigation of N2O on aftertreatment catalysts was shown to be ineffective as its formation and decomposition temperatures do not overlap. Therefore, the root causes for N2O formation were investigated to enable the catalyst architectures and controls development for minimizing its formation. In a typical heavy-duty diesel exhaust aftertreatment system based on selective catalytic reduction of NOx by ammonia derived from urea (SCR), the main contributors to tailpipe N2O are expected to be the undesired reaction between NOx and NH3 over SCR catalyst and NH3 slip in to ammonia slip catalyst (ASC), part of which gets oxidized to N2O.

The effects of propylene (C₃H₆) and dodecane (n-C₁₂H₂₆) exposure on the NH₃-based selective catalytic reduction (SCR) performance of two Cu-exchanged zeolite catalysts were investigated. The first sample was a model Cu/beta zeolite sample and the second a state-of-the-art Cu/zeolite sample, with the zeolite material characterized by relatively small pores. Overall, the state-of-the-art sample performed better than the model sample, in terms of hydrocarbon inhibition (which was reduced) and N₂O formation (less formed). The state-of-the-art sample was completely unaffected by dodecane at temperatures lower than 300°C, and only slightly inhibited (less than 5% conversion loss), for standard SCR, by C₃H₆. There was no evidence of coke formation on this catalyst with C₃H₆ exposure. The model sample was more significantly affected by hydrocarbon exposure. With C₃H₆, inhibition is associated with its partial oxidation intermediates adsorbed on the catalyst surface.

A typical diesel exhaust emission control system for meeting the US EPA 2010 regulations includes one or more platinum-group metal (PGM)-containing catalysts, located upstream of an SCR unit. However, as was previously reported in literature, under certain operating conditions PGM elements can get transferred onto the downstream SCR catalyst, resulting in the loss of its NOx conversion efficiency. In the same studies, the effect of Pt poisoning was found to be mitigated by catalyst treatment at 850°C, presumably due to Pt volatilization and migration. In the present study, we have explored the process of Pt poisoning mitigation, and identified that the recovery can take place at lower temperatures, reducing the risk of hydrothermal damage to the catalyst.

Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.