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Cu- and Fe-zeolite SCR catalysts emerged in recent years as the primary candidates for meeting the increasingly stringent lean exhaust emission regulations, due to their outstanding activity and durability characteristics. It is commonly known that Cu-zeolite catalysts possess superior activity to Fe-zeolites, in particular at low temperatures and sub-optimal NO₂/NOx ratios. In this work, we elucidate some underlying mechanistic differences between these two classes of catalysts, first based on their NO oxidation abilities, and then based on the relative properties of the two types of exchanged metal sites. Finally, by using the ammonia coverage-dependent NOx performance, we illustrate that state-of-the-art Fe-zeolites can perform better under certain transient conditions than in steady-state.

Cu/CHA catalysts have been widely used in the industry, due to their desirable performance characteristics including the unmatched hydrothermal stability. While broadly recognized for their outstanding activity at or above 200°C, these catalysts may not show desired levels of NOx conversion at lower temperatures. To achieve high NOx conversions it is desirable to have NO2/NOx close to 0.5 for fast SCR. However even under such optimal gas feed conditions, sustained use of Cu/CHA below 200°C leads to ammonium nitrate formation and accumulation, resulting in the inhibition of NOx conversion. In this contribution, the formation and decomposition of NH4NO3 on a commercial Cu/CHA catalyst have been investigated systematically. First, the impact of NH4NO3 self-inhibition on SCR activity as a function of temperature and NO2/NOx ratios was investigated through reactor testing.

A study was performed to assess the effects of the catalyst volume and the ceria content in the washcoat on the aged emission performance of underfloor catalytic converters containing platinum and rhodium. Catalyst volumes of 1.4 L and 2.8 L were evaluated, while the ceria level was varied from 0 to 60% of the weight of the washcoat. The concentration of noble metals (g/L) was the same for both catalyst volumes, so the larger volume also contained more noble metal. Catalyst performance was evaluated on an air/fuel ratio sweep test, at steady-state conditions on an engine, and on the FTP test. In light of the new catalyst monitoring requirements for OBD II, each catalyst was also evaluated at steady-state conditions using a dual oxygen sensor technique in order to produce an O2 sensor index. The evaluations were performed at several intermediate stages as the catalysts were aged on engines using high temperature durability schedules intended to simulate high mileage conditions.

Sustained NOx reduction at low temperatures, especially in the 150-200 °C range, shares some similarities with the more commonly discussed cold-start challenge, however, poses a number of additional and distinct technical problems. In this project, we set a bold target of achieving and maintaining 90% NOx conversion at the SCR catalyst inlet temperature of 150 °C. This project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015 and completed in 2017.

The low-temperature performance characteristics of a commercial lean NOX trap catalyst were evaluated using infra-red thermography (IRT) before and after a high-temperature aging step. Reaction tests included propylene oxidation, oxygen storage capacity measurements, and simulated cycling conditions for NOX reduction, using H₂ as the reductant during the regeneration step of the cycle. Testing with and without NO in the lean phase showed thermal differences between the reductant used in reducing the stored oxygen and that for nitrate decomposition and reduction. IRT clearly demonstrated where NOX trapping and regeneration were occurring spatially as a function of regeneration conditions, with variables including hydrogen content of the regeneration phase and lean- and rich-phase cycle times.

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.

Plug flow reactors, simulating engine exhaust gas, are widely used in emissions control research to gain insight into the reaction mechanisms and engineering aspects that controls activity, selectivity, and durability of catalyst components. The choice of relevant hydrocarbon (HC) species is one of the most challenging factor in such laboratory studies, given the variety of compositions that can be encountered in different application scenarios. Furthermore, this challenge is amplified by the experimental difficulties related to introducing heavier and multi-component HCs and analyzing the reaction products.

Lean NOx Traps (LNTs) are one type of lean NOx reduction technology typically used in smaller diesel passenger cars where urea-based Selective Catalytic Reduction (SCR) systems may be difficult to package . However, the performance of lean NOx traps (LNT) at temperatures above 400 C needs to be improved. The use of Rapidly Pulsed Reductants (RPR) is a process in which hydrocarbons are injected in rapid pulses ahead of a LNT in order to expand its operating window to higher temperatures and space velocities. This approach has also been called Di-Air (diesel NOx aftertreatment by adsorbed intermediate reductants) by Toyota. There is a vast parameter space which could be explored to maximize RPR performance and reduce the fuel penalty associated with injecting hydrocarbons. In this study, the mixing uniformity of the injected pulses, the type of reductant, and the concentration of pulsed reductant in the main flow were investigated.

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.

Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.

The high global warming potential of nitrous oxide (N₂O) led to its recent inclusion in the list of regulated pollutants under the emerging greenhouse gas regulations. While N₂O can be present in small quantities among the combustion products, it can also be generated as a minor byproduct in various types of aftertreatment systems. In this work, a systematic review of sources of N₂O is presented, along with the potential mechanisms of formation in a typical selective-catalytic-reduction-based diesel exhaust aftertreatment system. It is demonstrated that diesel oxidation catalysts (DOC), selective catalytic reduction (SCR) catalyst, and ammonia slip catalyst (ASC) can all potentially contribute to N₂O formation, depending on the catalyst material and exhaust gas conditions, as well as aftertreatment operation strategies. Furthermore, catalysts used in SCR aftertreatment system are also shown to decompose and/or reduce N₂O to N₂ under select conditions.

This paper presents a monitoring, feedback and control system for SCR urea dosing utilizing an embedded model and NH3 sensing after the SCR for loop closing control. A one-dimensional SCR model was developed and embedded in a Simulink/Matlab environment. This embedded model is utilized for on-line, real time control of 32.5% aqueous urea dosing in the exhaust stream. Engine testing and simulation are used with the embedded SCR model and NH3 sensor closed loop feedback to demonstrate the advantages of this control approach for meeting both NOx emission requirements and NH3 slip targets. The paper explores these advantages under heavy duty FTP cycle conditions. The potential benefits include SCR size optimization and fuel consumption rate reduction under certain operating conditions.

Several reactor systems have been used to study the catalytic chemistry of a particular proprietary zeolitic catalyst in conditions that mimic those found in light-duty diesel exhaust after a non-thermal plasma generator. Very similar catalytic results were obtained with NO + plasma or NO2 as the source of NOx using propene (C3H6) as the reductant. The formation of nitrogen, carbon dioxide, and other products were studied from 150°C to 250°C using a He balance gas and NOx in the form of NO2. The results demonstrate that nitrogen is formed by the selective catalytic reduction of NO2 by propene. The highest activity for N2 formation from NO2 was near 50% conversion at 200°C for a space velocity of 12,600 h-1. The NOx conversion by adsorption and by catalytic reduction was quantified. By performing studies with and without the presence of water, a clear separation in behavior between adsorption processes and catalytic reaction was observed.

Oxygen storage capacity (OSC) is one of the most critical characteristics of a three-way catalyst (TWC) and is closely related to the catalyst aging and performance. In this study, a dynamic OSC model involving two oxygen storage sites with distinct kinetics was developed. The dual-site OSC model was validated on a bench reactor and a natural gas engine. The model was capable of predicting temperature dependence on OSC with H2, CO and CH4 as reductants. Also, the effects of oxygen concentration and space velocity on the amount of OSC were captured by the model. The validated OSC model was applied to simulate lean breakthrough phenomena with varied space velocities and oxygen concentrations. It is found that OSC during lean breakthrough is not a constant for a particular TWC catalyst and is dependent on space velocity and oxygen concentration. Specifically, breakthrough time exhibits a non-linear, inverse correlation to oxygen flux.

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.

Typical Lean NOx Trap (LNT) catalyst composition includes precious metal components (Pt, Pd, and/or Rh), responsible for NO oxidation during lean operation and NOx reduction during rich operation. It was found that redox history of commercial LNT catalyst plays a significant role on deciding its NOx conversion under Lean/Rich cyclic condition. Further test had shown that fully formulated LNT catalyst being pre-reduced had shown much better NO reduction activity during the temperature-programmed reduction (TPRx) of NO than the same LNT catalyst being oxidized. The following study with Rh-only and Pt-only catalyst had demonstrated that Rh plays a key role on the large variation of the NO reduction function due to oxidation state change over LNT catalyst.

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.

In this contribution, nuanced changes of a commercial Cu-SSZ-13 catalyst with hydrothermal aging, which have not been previously reported, as well as their corresponding impact on SCR functions, are described. In particular, a sample of Cu-SSZ-13 was progressively aged between 550 to 900°C and the changes of performance in NH3 storage, oxidation functionality and NOx conversion of the catalyst were measured after hydrothermal exposure at each temperature. The catalysts thus aged were further characterized by NH3-TPD, XRD and DRIFTS techniques for structural changes. Based on the corresponding performance and structural characteristics, three different regimes of hydrothermal aging were identified, and tentatively as assigned to “mild”, “severe” and “extreme” aging. Progressive hydrothermal aging up to 750°C decreased NOx conversion to a small degree, as well as NH3 storage and oxidation functions.

In this study we investigated the interaction of short- and long-chain hydrocarbons (HCs), represented by propene (C₃H₆) and n-dodecane (n-C₁₂H₂₆), respectively, with a state-of-the-art small-pore Cu-Zeolite SCR catalyst. By varying HC adsorption conditions, we determined that physisorption was the primary mechanism for some minor HC storage at low temperatures (≺ 200°C), while chemical transformation was involved in more substantial HC storage at higher temperatures (200-400°C). The latter was evidenced by the oxygen-dependent and thermally activated nature of the storage process, and further confirmed by the carbon-rich composition of the deposits. The nature of HC-derived deposits of different origins and amounts was further probed using the standard SCR reaction at kinetically challenging conditions (at 200°C), as well by ammonia adsorption/desorption experiments.

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.