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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.

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.

A 1-dimensional analytic solution has been developed to evaluate the pressure drop and filtration performance of ceramic wall-flow partial diesel particulate filters (PFs). An axially resolved mathematical model for the static pressure and velocity profiles prevailing inside wall-flow filters, with such unique plugging configurations, is being proposed for the first time. So far, the PF models that have been developed are either iterative/numerical in nature [1], or based on commercial CFD packages [7]. In comparison, an analytic solution approach is a transparent and computationally inexpensive tool that is capable of accurately predicting trends as well as, offering explanations to fundamental performance behavior. The simple mathematical expressions that have been obtained facilitate rational decision-making when designing partial filters, and could also reduce the complexity of OBD logic necessary to control onboard filter performance.

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.

Copper- and Iron- based metal-zeolite SCR catalysts are widely used in US and European diesel aftertreatment systems to achieve drastic reduction in NOx emission. These catalysts are highly selective to N2 under wide range of operating conditions. Nevertheless, the type of transition metal has a significant impact on the key performance and durability parameters such as NOx conversion, selectivity towards N2O, hydrothermal stability, and sensitivity to fuel sulfur content. In this study, we explained the differences in the performance characteristics of these catalysts based on their relative acidic-basic nature of transition metal present in these catalysts using practically relevant gas species present in diesel exhaust such as NO2, SOx, and NH3. These experiments show that Fe-zeolite has relatively acidic nature as compared to Cu-zeolite that causes NH3 inhibition and hence explains low NOx conversion on Fe-zeolite at low temperature under standard SCR conditions.

Regeneration of diesel particulate filters poses major challenges in developing the particulate matter emission control technology to meet EPA 2007/2010 emissions regulations. The problem areas are multifold due to the complexity involved in designing the filter system, developing regeneration strategies and controlling the regeneration process. This paper discusses the need for active regeneration systems. It also addresses several key limitations and trade-offs between the regeneration strategy, chemical kinetics, exhaust gas temperature and the regeneration efficiency. Passive regeneration of diesel particulate filter systems is known to be highly dependent on the engine-out [NOx/PM] ratio as well as exhaust temperature over the duty cycle. Using catalytic oxidation of auxiliary fuel injected into the system, the exhaust gas temperature can be successfully enhanced for filter regeneration.

In this work, an alternative method is proposed and validated for quantifying the axial performance of a state-of-the-art Cu zeolite SCR catalyst. Catalyst cores of a standard length, with varying lengths of wash-coated regions were used to axially resolve the functional performance of the SCR catalyst. This proposed method was validated by quantifying the catalyst entrance and exit effects, as well as the effect of non-uniform wash-coat loading densities. This method is less susceptible to some of the complications highlighted in the previous studies, such as flow uniformity between channels, as well as radiative heating effects, since the product gases are sampled across the entire monolith cross-section rather than through a single catalyst channel. The specific catalyst functions quantified include: NO and NH₃ oxidation, NH₃ storage capacity, as well as NOx conversion efficiency.

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.

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.

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.

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.

The operation of NOx Adsorber catalysts (NAC), also often referred to as Lean NOx Trap catalysts or NOx Storage-reduction catalysts, entails frequent periodic NOx regeneration events. These are accomplished by creating a net reducing, fuel-rich environment in the exhaust. The reduction of hydrocarbon emissions which occur during such fuel-rich events is challenging, due to the oxygen-deficient environment. In order to overcome this limitation, two possibilities exist: (i) oxygen can be stored during lean phase, to be used for hydrocarbon slip oxidation in the subsequent rich phase, or (ii) unreacted hydrocarbons can be trapped during the rich phase and oxidized during the following lean phase. In this work, two groups of catalytic solutions were developed and evaluated for hydrocarbon emission control based on these approaches: an Oxygen Storage Compound (OSC) based catalyst and zeolite-based hydrocarbon trap catalyst.

Commercial Cu-Zeolite SCR catalyst can store and subsequently release significant amount of H2O. The process is accompanied by large heat effects. It is critical to model this phenomenon to design aftertreatment systems and to provide robust tuning strategies to meet cold start emissions and low temperature operation. The complex reaction mechanism of water adsorption and desorption over a Cu-exchanged SAPO-34 catalyst at low temperature was studied through steady state and transient experiments. Steady state isotherms were generated using a gravimetric method and then utilized to predict water storage interactions with respect to feed concentration and catalyst temperature. Transient temperature programmed desorption (TPD) experiments provided the kinetic information required to develop a global kinetic model from the experimental data. The model captures fundamental characteristics of water adsorption and desorption accompanied by the heat effects.

Oxidation of NO to NO₂ over a Diesel Oxidation Catalyst (DOC) plays an important role in different types of aftertreatment systems, by enhancing NOx storage on adsorber catalysts, improving the NOx reduction efficiency of SCR catalysts, and enabling the passive regeneration of Diesel Particulate Filters (DPF). The presence of hydrocarbon (HC) species in the exhaust is known to affect the NO oxidation performance over a DOC; however, specific details of this effect, including its underlying mechanism, remain poorly understood. Two major pathways are commonly considered to be responsible for the overall effect: NO oxidation inhibition, due to the presence of HC, and the consumption of the NO₂ produced by reaction with hydrocarbons. In this work we have attempted to decouple these two pathways, by adjusting the catalyst inlet concentrations of NO and NO₂ to the thermodynamic equilibrium levels and measuring the composition changes over the catalyst in the presence of HC species.

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.

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.