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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.

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.

Gasoline direct injection (GDI) engines have become very attractive in transportation due to several benefits over preceding engine technologies. However, GDI engines are associated with higher levels of particulate matter (PM) emissions, which is a major concern for human health. The aim of this work is to broaden the understanding of the effect of hydrogen combustion and the influence of the three way catalytic converter (TWC) on PM emission characteristics. The presence of hydrogen in GDI engines has been reported to reduce fuel consumption and improve the combustion process, making it possible to induce higher rates of EGR. A prototype exhaust fuel reformer build for on-board vehicle hydrogen-rich gas (reformate) production has been integrated within the engine operation and studied in this work.

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.

The use of catalyzed diesel particulate filter (CDPF) systems in light duty diesel (LDD) vehicles is becoming increasingly common. The primary functions of the system are to remove carbon monoxide (CO) and hydrocarbons (HC) from the vehicle exhaust stream, while simultaneously reducing the level of particulate matter (PM) emissions to ambient background levels. These systems can comprise either a separate diesel oxidation catalyst (DOC) and a downstream CDPF, or a single unit CDPF with the DOC functions incorporated within the CDPF. The single CDPF unit provides higher regeneration efficiency as it is located nearer to the engine and also cost benefits, as only a single unit is required compared to the alternative separate DOC and CDPF arrangement. A model describing the performance of the single unit CDPF for emissions control has been developed, with particular emphasis on achieving predictions of the CO and HC emissions over transient vehicle drive cycles.

Particulate Matter (PM) emissions are of increasing importance, as diesel emissions legislation continues to tighten around the world. Diesel PM can be controlled using Diesel Particulate Filters (DPFs), which can effectively reduce the level of carbon (soot) emissions to ambient background levels. The Johnson Matthey Continuously Regenerating Trap (CRT®) [1], which will be referred to as the Continuously Regenerating DPF (CR-DPF) for the remainder of this paper, has been widely applied in Heavy Duty Diesel (HDD) applications, and has been proved to have outstanding field durability [2]. To widen the potential application of this system, addition of a platinum based catalyst to the DPF has been shown to lead to a higher PM removal rate under passive regeneration conditions, using the NOx contained in the exhaust gases.

The aftertreatment challenge in the non-road market is making the same system work and fit not just in one machine, but in hundreds of different machines, some of which can be used for many different purposes. This huge diversity of applications and the relatively small unit numbers for each application, coupled with the rapid introduction of new standards and the very high performance needed from the engines and machines, requires a sophisticated approach to product development. Furthermore, as emissions requirements become ever more stringent, designing a system to meet the legislation subject to packaging and cost constraints becomes progressively more difficult. This is further exacerbated by increasing system complexity, where more than one technology may be required to control all the legislated pollutants and/or an active control strategy is involved. Also a very high degree of component integration is required.

A 1-D numerical model describing the ammonia selective catalytic reduction (SCR) de-NOx process has been developed based on data measured on a laboratory microreactor for a vanadia-titania washcoated catalyst system. Kinetics for various NH3-NOx reactions were investigated, as well as those for ammonia, CO and hydrocarbon oxidation. The model has been successfully validated against engine bench measurements, over light-off and ESC tests, under a wide range of conditions, e.g. flow rate, temperature, NO2/NO ratio, and ammonia injection rate. A very good agreement between the experimental data and the model has been achieved. The model has now been used to predict the effect of NO2/NO ratio on NOx conversion, and the effect of different ammonia injection rates on the efficiency of the SCR process.

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.

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.

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.

Several complementary experimental techniques were applied to investigate kinetics of diesel soot oxidation by O2 in an attempt to provide accurate data for modeling of the Diesel Particulate Filters regeneration process. For two diesel soot samples with measurably different properties, it was shown that the complexity of their overall kinetic behavior was due to an initial period of rapidly changing reactivity. This initial high reactivity was understood not to be related to the SOF, and was quantitatively correlated to the extent of soot pre-oxidation. This initial reactivity can affect the averaged apparent kinetic parameters, for example resulting in the lower apparent activation energy values. After the initial soot pre-oxidation, which consumed ∼10-25% of carbon, the remaining soot was behaving very uniformly, producing linear Arrhenius plots in a remarkably broad range of temperatures (330-610°C) and integral conversions (up to 90%).