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The steam reforming of CH4 plays a crucial role in the high-temperature activity of natural gas three-way catalysts. Despite existing reports on sulfur inhibition in CH4 steam reforming, there is a limited understanding of sulfur storage and removal dynamics under various lambda conditions. In this study, we utilize a 4-Mode sulfur testing approach to elucidate the dynamics of sulfur storage and removal and their impact on three-way catalyst performance. We also investigate the influence of sulfur on CH4 steam reforming by analyzing CH4 conversions under dithering, rich, and lean reactor conditions. In the 4-Mode sulfur test, saturating the TWC with sulfur at low temperatures emerges as the primary cause of significant three-way catalyst performance degradation. After undergoing a deSOx treatment at 600 °C, NOx conversions were fully restored, while CH4 conversions did not fully recover.

The prediction accuracy of a three-way catalyst (TWC) model is highly associated with the ability of the model to incorporate the reaction kinetics of the emission process as a lambda function. In this study, we investigated the O2 and H2 concentration profiles of TWC reactions and used them as critical inputs for the development of a global TWC model. We presented the experimental data and global kinetic model showing the impact of thermal degradation on the performance of the TWC. The performance metrics investigated in this study included CH4, NOx, and CO conversions under lean, rich, and dithering light-off conditions to determine the kinetics of oxidation reactions and reduction/reforming/water-gas shift reactions as a function of thermal aging. The O2 and H2 concentrations were measured using mass spectrometry to track the change in the oxidation state of the catalyst and to determine the mechanism of the reactions under these light-off conditions.

Upcoming, stricter diesel exhaust emissions standards will likely require aftertreatment architectures with multiple diesel exhaust fluid (DEF) introduction locations. Managing NH3 slip with technologies such as an ammonia slip catalyst (ASC) will continue to be critical in these future aftertreatment systems. In this study, we evaluate the impact of SO2 exposure on a state-of-the-art commercially available ASC. SO2 is co-fed at 0.5 or 3 ppmv to either approximate or accelerate a real-world exhaust SO2 impact. ASC performance during sulfur co-feeding is measured under a wide variety of simulated real-world conditions. Results indicate that the loss of NO conversion during SCR is dependent on the cumulative SO2 exposure, regardless of the inlet SO2 concentration. Meanwhile, N2O formation under SCR conditions is nonlinearly affected by SO2 exposure, with formation increasing during 0.5 ppmv SO2 exposure but decreasing in the presence of 3 ppmv SO2.

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.

Cu-SSZ-13 selective catalytic reduction (SCR) catalysts are broadly applied in diesel aftertreatment systems for the catalytic conversion of oxides of nitrogen (NO + NO2). Diesel exhaust contains a wide range of water vapor concentrations depending on the operating condition. In this study, we evaluate the impact of water vapor on the relevant SCR catalytic functions including NOx conversion, NO oxidation, NH3 oxidation, and N2O formation under both standard and fast SCR conditions. Reactor-based experiments are conducted in the presence and absence of water vapor. Results indicate that water vapor can have both a positive and negative impact on low temperature NOx conversion for standard SCR reaction. At low inlet NOx concentrations, the presence of water vapor has a negative effect on NOx conversion, whereas, at high inlet NO concentrations, water vapor improves NOx conversion.

The measurement of solid particles down to 10 nm is being incorporated into global technical regulations (GTR). This study explores the measurement of solid particles below 23 nm by using both current and proposed particle number (PN) systems having different volatile particle remover (VPR) methodologies and condensation particle counter (CPC) cutoff diameters. The measurements were conducted in dynamometer test cells using ten diesel and eight natural gas (NG) engines that were going under development for a variety of global emission standards. The PN systems measured solid PN from more than 700 test cycles. The results from the preliminary campaign showed a 10-280% increase in PN emissions with the inclusion of particles below 23 nm.

The present study examines the impact of using low thermal mass (LTM) turbine housing designs on the transient characteristics of the turbine outlet temperature for a light-duty diesel standard certification cycle (FTP75). For a controlled exhaust flow, the turbine outlet temperature will directly determine the impact on an aftertreatment system warm-up from a cold state, typical of engine-off and engine idling conditions. The performance of the aftertreatment system such as a Selective Catalytic Reduction (SCR) system is highly dependent on how quickly it warms up to its desirable temperature to be able to convert the harmful oxides of Nitrogen (NOx) to gaseous Nitrogen. Previous works have focused on mostly insulating the exhaust manifold and turbine housing to conserve the heat going into the aftertreatment system. The use of LTM turbine housing has not been previously considered as a means for addressing this requirement.

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.

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.

Effective control of exhaust emissions from modern diesel engines requires the use of aftertreatment systems. Elevated aftertreatment component temperatures are required for engine-out emissions reductions to acceptable tailpipe limits. Maintaining elevated aftertreatment components temperatures is particularly problematic during prolonged low speed, low load operation of the engine (i.e. idle, creep, stop and go traffic), on account of low engine-outlet temperatures during these operating conditions. Conventional techniques to achieve elevated aftertreatment component temperatures include delayed fuel injections and over-squeezing the turbocharger, both of which result in a significant fuel consumption penalty. Cylinder deactivation (CDA) has been studied as a candidate strategy to maintain favorable aftertreatment temperatures, in a fuel efficient manner, via reduced airflow through the engine.

Countries around the world are expected to continue to adopt more stringent emissions standards for heavy-duty markets for both oxides of nitrogen (NOx) and greenhouse gases (GHG). While there is uncertainty about the timing and extent of these regulations, it is clear that significant reductions will be required to address urban air pollution and climate change concerns. The rate and pace of technology evolution and how it will affect the energy pathways for commercial transportation and industrial use are dependent on multiple variables such as national energy and environmental policies and public-private partnerships. Although it adds complexity, the engine system has great potential to evolve as it continues to be highly integrated into the super system for which it is producing power. This paper examines the potential opportunities and challenges for engine manufacturers to continue to be the supplier of power to vehicles and equipment of the future.

Future light duty vehicles in the United States are required to be certified on the FTP-75 cycle to meet Tier 3 or LEV III emission standards [1, 2]. The cold phase of this cycle is heavily weighted and mitigation of emissions during this phase is crucial to meet the low tail pipe emission targets [3, 4]. In this work, a novel aftertreatment architecture and controls to improve Nitrogen Oxides (NOx) and Hydrocarbon (HC) or Non Methane Organic gases (NMOG) conversion efficiencies at low temperatures is proposed. This includes a passive NOx & HC adsorber, termed the diesel Cold Start Concept (dCSC™) catalyst, followed by a Selective Catalytic Reduction catalyst on Filter (SCRF®) and an under-floor Selective Catalytic Reduction catalyst (SCR). The system utilizes a gaseous ammonia delivery system capable of dosing at two locations to maximize NOx conversion and minimize parasitic ammonia oxidation and ammonia slip.

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.

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.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

Exposure of hydrocarbons (HCs) and particulate matter (PM) under certain real-world operating conditions leads to carbonaceous deposit formation on V-SCR catalysts and causes reversible degradation of its NOx conversion. In addition, uncontrolled oxidation of such carbonaceous deposits can also cause the exotherm that can irreversibly degrade V-SCR catalyst performance. Therefore carbonaceous deposit mitigation strategies, based on their characterization, are needed to minimize their impact on performance. The nature and the amount of the deposits, formed upon exposure to real-world conditions, were primarily carried out by the controlled oxidation of the deposits to classify these carbonaceous deposits into three major classes of species: i) HCs, ii) coke, and iii) soot. The reversible NOx conversion degradation can be largely correlated to coke, a major constituent of the deposit, and to soot which causes face-plugging that leads to decreased catalyst accessibility.

The interest for NOx estimators (also known as virtual sensors or inferential sensors) has increased over the recent years due to benefits attributed to cost and performance. NOx estimators are typically installed to improve On-Board Diagnostics (OBD) monitors or to lower bill of material costs by replacing physical NOx sensors. This paper presents initial development results of a virtual engine-out NOx estimator planned for the implementation on an ECM. The presented estimator consists of an airpath observer and a NOx combustion model. The role of the airpath observer is to provide input values for the NOx combustion model such as the states of the gas at the intake and exhaust manifolds. It contains a nonlinear mean-value model of the airpath suitably transformed for an efficient and robust implementation on an ECM. The airpath model uses available sensory information in the vehicle to correct predictions of the gas states.

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.

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 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.