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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.

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.

Future emissions regulations proposed for the Asian automotive industry (BS VI regulations for India and NS VI regulations for China) are strict and similar to EU VI regulations. As a result, they will require both advanced NOx control as well as advanced Particulate Matter (PM) control. This will drive implementation of full Catalyzed Diesel Particulate Filter (cDPF) and simultaneous NOx control using Selective Catalytic Reduction (SCR) technologies. In this work, we present the performance of various Diesel Oxidation Catalyst (DOC), cDPF, SCR and Ammonia slip catalyst (ASC) systems utilizing the World Harmonized Transient Cycle (WHTC). Aftertreatment Systems (ATS) required for both active and passive filter regeneration applications will be discussed. The sensitivity of key design parameters like catalyst technology, PGM loading, catalyst sizing to meet the regulation limits has been investigated.

The phase-in of US EPA Tier 3 and California LEV III emission standards require further reduction of tailpipe criteria pollutants from automobiles. At the same time, the mandate for reducing Green House Gas (GHG) emissions continuously lowers the exhaust temperature. Both regulations pose significant challenges to emission control catalyst technologies, especially for cold start emissions. The recently developed diesel cold start concept technology (dCSC™) shows promising results. It stores NOx and HC during the cold start period until the downstream catalytic components reach their operating temperatures, when the stored NOx/HC are subsequently released and converted. The technology also has oxidation functions built in and acts as a diesel oxidation catalyst under normal operating conditions. In a US DOE funded project, the diesel cold start concept technology enabled a high fuel efficiency vehicle to achieve emissions targets well below the SULEV30 emission standards.

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.

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.

Microreactor, engine bench tests and modelling studies have been carried out to understand the influence of cold start (low temperatures) on the performance of NH3/urea-SCR automotive exhaust aftertreatment systems. Water storage experiments using Simultaneous Thermal Analysis (STA) coupled with numerical modelling demonstrated that the exo/endo-therms associated with water adsorption and desorption at temperatures below 150°C strongly influence the catalyst temperature. Appreciable amounts of NO and NO2 could be stored on the catalyst during reactor or engine testing in the absence of any NH3 (blank tests). Modelling studies at different inlet NO2/NOx ratios demonstrated some of the influences of these surface adsorbed species on the performance of the SCR system during cold start.

Selective Catalytic Reduction (SCR) systems have been demonstrated as effective solutions for controlling NOx emissions from Heavy Duty diesel engines. Future HD diesel engines are being designed for higher engine out NOx to improve fuel economy, while discussions are in progress for tightening NOx emissions from HD engines post 2020. This will require increasingly higher NOx conversions across the emission control system and will challenge the current aftertreatment designs. Typical 2010/2013 Heavy Duty systems include a diesel oxidation catalyst (DOC) along with a catalyzed diesel particulate filter (CDPF) in addition to the SCR sub-assembly. For future aftertreatment designs, advanced technologies such as cold start concept (dCSC™) catalyst, SCR coated on filter (SCRF® hereafter referred to as SCR-DPF) and SCR coated on high porous flow through substrates can be utilized to achieve high NOx conversions, in combination with improved control strategies.

This paper presents a two-part study on the effect of Pt:Pd ratio (at a constant total Pt+Pd loading of 120 g ft−3) on the catalytic performance of a Diesel Oxidation Catalyst (DOC) intended for light-duty applications, covering ratios across the full range from 100% Pd to 100% Pt. (Work on a heavy-duty DOC is presented in SAE 2015-01-1052). The first part of this paper presents a reactor study on the effect of Pt:Pd ratio on the catalytic activity of key reactions occurring individually over the DOC, including the oxidation of CO, C3H6, n-C10H22, CH4 and NO. For some reactions, activity increases continuously with Pt content (oxidation of n-C10H22 and NO); in contrast the activity for CH4 oxidation increases with decreasing Pt content (increasing Pd content), while CO and C3H6 oxidation exhibit more complicated dependencies. The second part presents the development of a one-dimensional model capable of predicting the effect of Pt:Pd ratio on DOC performance.

Selective Catalytic Reduction (SCR) catalysts have been demonstrated as an effective solution for controlling NOx emissions from diesel engines. There is a drive to reduce the overall packaging volume of the aftertreatment system for these applications. In addition, more active SCR catalysts will be needed as the applications become more challenging: e.g. lower temperatures and higher engine out NOx, for fuel consumption improvements. One approach to meet the challenges of reduced volume and/or higher NOx reduction is to increase the active site density of the SCR catalyst by coating higher amount of SCR catalyst on high porosity substrates (HPS). This approach could enable the reduction of the overall packaging volume while maintaining similar NOx conversion as compared to 2010/2013 systems, or improve the NOx reduction performance for equivalent volume and NH3 slip.

Stricter emission standards in the near future require not only a high conversion efficiency of the toxic air pollutants but also a substantial reduction of the greenhouse gases from automotive exhaust. Advanced engines with improved fuel efficiency can reduce the greenhouse gas emissions; their exhaust temperature is, however, also low. This consequently poses significant challenges to the emission control system demanding the catalysts to function at low temperatures both during the cold start period and under the normal engine operation conditions. In this paper, we will introduce a gasoline Cold Start Concept (gCSC™) technology developed for advanced stoichiometric-burn gasoline engines to meet future stringent emission regulations. To improve the low temperature performance of three-way catalysts, a novel Al2O3/CeO2/ZrO2 mixed oxide was developed.

Selective Catalytic Reduction (SCR) systems have been demonstrated as effective solutions for controlling NOx emissions from Heavy Duty diesel engines. Future HD diesel engines are being designed for higher engine out NOx to improve fuel economy, which will require increasingly higher NOx conversion to meet emission regulations. For future aftertreatment designs, advanced technologies such as SCR coated on filter (SCRF®) and SCR coated on high porous flow through substrates can be utilized to achieve high NOx conversion. In this work, different options were evaluated for achieving high NOx conversion. First, high performance NOx control catalysts were designed by using SCRF unit followed by additional SCR on high porosity substrates. Second, different control strategies were evaluated to understand the effect of reductant dosing strategy and thermal management on NOx conversion. Tests were carried out on a HD engine under transient test cycles.

Achieving early catalyst light-off is crucial if stringent emissions standards are to be met; if light-off is late, the emissions limit could be exceeded even before the catalyst starts to work. This paper presents a detailed simulation study of the factors affecting the light-off of a TWC. Simulation is not just faster and cheaper than vehicle testing, it also enables more insight into the factors affecting catalyst performance to be obtained. For example, changing the substrate (cell density and wall thickness) affects the rates of heat and mass transport, as well as the thermal mass of the catalyst. In a vehicle test, all three factors are changed at once, but with a simulation each of these factors can implemented one at time to enable the relative importance of these factors to be determined.

The use of vanadia selective catalytic reduction (V-SCR) catalysts for NOX reduction from diesel engine exhaust is well known. These catalysts are also active for hydrocarbon (HC) and particulate matter (PM) oxidation. This dual functionality (oxidation and reduction) of V-SCR catalysts can help certain applications achieve the legislative limits with an improved margin. In this work, NOX reduction, HC and CO oxidation over V-SCR were studied independently and simultaneously in microreactor tests. The effect of various parameters (HC speciation, concentration, ANR, and NO₂/NOX ratio) was investigated and the data was used to develop a kinetic model. Oxidation of CO, C₃H₆, and n-C₁₀H₂₂ is first order in CO/HC, while C₇H₈ oxidation is less than first order in C₇H₈. All these reactions were zero order in O₂. Oxidation activity decreased in order: C₇H₈ ≻ n-C₁₀H₂₂ ≻ C₃H₆ ≻ CO. HC oxidation was inhibited by NH₃.

Catalytic emission control systems are installed on nearly all automobiles and heavy-duty trucks produced today to reduce exhaust emissions for the vehicles to meet government regulations. Current systems can achieve very high efficiencies in reducing tailpipe emissions once the catalytic components reach their operating temperatures. They are, however, relatively ineffective at temperatures below their operating temperature windows, especially during the cold start period of the vehicles. With the increasingly stringent government regulations, reducing the emissions during the cold start period before the catalytic components reach their operating temperatures is becoming a major challenge. For cold start HC control, HC traps based on zeolites have been investigated and commercialized for certain applications. For cold start NOx control, especially in lean burn engine exhaust, NOx storage and release catalysts have been evaluated.

In recent years, ammonia slip catalysts (ASC) are being used downstream of an SCR system to minimize the ammonia slip. The dual-layer ASC is more attractive for its bi-functionality in reducing the ammonia and NOX emissions. It consists of two layers with the upper layer comprising a component with SCR functionality and the lower layer a PGM containing catalyst with oxidation functionality. Thus, both oxidation and SCR reactions take place in two different layers and are interlinked by the inter-layer mass transfer mechanism. In addition, adsorption and desorption kinetics between the gas and solid phases play a significant role. Mathematically, the overall system is a complex system of mass, momentum and energy transfer equations with temporal and spatial variables in both axial and radial directions. In this work, we focus on devising a suitable, computationally inexpensive model for such ASCs to be efficiently used for design, control and system optimization studies.

In earlier work we have shown that engine operation with oxygenated fuels (e.g., biodiesel) reduces the particulate matter (PM) emissions and extends the engine tolerance to exhaust gas recirculation (EGR) before it reaches smoke limited conditions. The same result has also been reported when high cetane number fuels such as gas-to-liquid (GTL) are used. A likely mechanism for engine-out particulate growth is the reintroduction of particle nuclei into the cylinder through EGR. These recirculated PM particles serve as sites for further condensation and accumulation promoting larger and greater number of particles. In order to further our understanding of EGR influence on total PM production, a diesel particulate filter (DPF) was integrated into the EGR loop. A PM reduction of approximately 50% (soot) was achieved with diesel fuel through filtered EGR, whilst still maintaining a significant NOX reduction.

Computational Fluid Dynamics (CFD) is used to simulate chemical reactions and transport phenomena occurring in a single channel of a honeycomb-type automotive catalytic converter under lean burn combustion. Microkinetic analysis is adopted to develop a detailed elementary reaction mechanism for propane oxidation on a silver catalyst. Activation energies are calculated based on the theory of the Unity Bond Index-Quadratic Exponential Potential (UBI-QEP) method. The order-of-magnitude of the pre-exponential factors is obtained from Transition State Theory (TST). Sensitivity analysis is applied to identify the important elementary steps and refine the pre-exponential factors of these reactions. These pre-exponential factors depend on inlet temperatures and propane concentration; therefore optimised pre-exponential factors are written in polynomial forms. The results of numerical simulations are validated by comparison with experimental data.

Selective Catalytic Reduction (SCR) catalysts have been demonstrated as an effective solution for controlling NOx emissions from diesel engines. Typical 2010 Heavy-Duty systems include a DOC along with a catalyzed soot filter (CSF) in addition to the SCR sub-assembly. There is a strong desire to further increase the NOx conversion capability of such systems, to enable additional fuel economy savings by allowing engines to be calibrated to higher engine-out NOx levels. One potential approach is to replace the CSF with a diesel particulate filter coated with SCR catalysts (SCR-DPF) while keeping the flow-through SCR elements downstream, which essentially increases the SCR volume in the after-treatment assembly without affecting the overall packaging. In this work, a system consisting of SCR-DPF was evaluated in comparison to the DOC + CSF components from a commercial 2010 DOC + CSF + SCR system on an engine with the engine EGR on (standard engine-out NOx) and off (high engine-out NOx).

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.