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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.

Light duty vehicle emission standards are getting more stringent than ever before as stipulated by US EPA Tier 2 Standards and LEV III regulations proposed by CARB. The research in this paper sponsored by US DoE is focused towards developing a Tier 2 Bin 2 Emissions compliant light duty pickup truck with class leading fuel economy targets of 22.4 mpg “City” / 34.3 mpg “Highway”. Many advanced technologies comprising both engine and after-treatment systems are essential towards accomplishing this goal. The objective of this paper would be to discuss key engine technology enablers that will help in achieving the target emission levels and fuel economy. Several enabling technologies comprising air-handling, fuel system and base engine design requirements will be discussed in this paper highlighting both experimental and analytical evaluations.

The increasing severity in emission standards around the world has been accompanied by the development of more active, durable catalysts. With a view to investigating the effects of high thermal aging on the catalyst performance and structure, the relationships of washcoat composition, washcoat structure, and PGM location with respect to catalyst activity were clarified using a model gas test, as well as physical and chemical characterization methods. The influence of newly developed washcoat components and PGM location on catalyst performance are also demonstrated by engine bench tests. The results obtained in this study indicate the newly developed Pt/Rh catalyst techologies are appropriate for future applications in which the catalyst will be exposed to extremely high temperature and flowrates.

Selective Catalytic Reduction (SCR) of oxides of nitrogen (NOx) with ammonia gas has established itself as an effective diesel aftertreatment technology to meet stringent emission standards enforced by worldwide regulatory bodies. Typically, in this technology, aqueous urea solution of eutectic composition - known as Diesel Exhaust Fluid (DEF) - is injected into hot exhaust gases leading to a series of thermal, fluid dynamic and reactive processes that eventually produces the ammonia necessary for NOx reduction reactions within monolithic catalytic substrates. Incomplete decomposition of the injected urea can lead to formation of solid deposits that adversely affect system performance by increasing the engine back pressure, reducing de-NOx efficiency, and lowering the overall fuel economy.

New advanced Pd only, Pd:Rh and Pt:Pd:Rh catalysts are compared with a current platinum rhodium catalyst after poisoning and thermal ageing. The results indicate that at equivalent precious metal cost (at 1994 prices) the advanced palladium based catalysts achieve significantly improved performance compared with current Pt, Rh and Pd technology. The new Pd:Rh formulation is recommended for close coupled locations and the Pt:Pd:Rh formulation recommended for underfloor locations where residual fuel lead may be present. The formation of H2S is shown to be low with the palladium based catalysts. Finally, it is shown that the new catalysts with balanced oxidation and reduction capability perform better in multi-brick systems than addition of a highly loaded palladium only front brick.

Diesel oxidation catalyst (DOC) is one of the critical catalyst components in modern diesel aftertreatment systems. It mainly converts unburned hydrocarbon (HC) and CO to CO2 and H2O before they are released to the environment. In addition, it also oxidizes a portion of NO to NO2, which improves the NOx conversion efficiency via fast SCR over the downstream selective catalytic reduction (SCR) catalyst. HC light-off tests, with or without the presence of NOx, has been typically used for DOC evaluation in laboratory. In this work, we aim to understand the influences of DOC light-off experimental conditions, such as initial temperature, initial holding time, HC species, with or without the presence of NOx, on the DOC HC light-off behavior. The results indicate that light-off test with lower initial temperature and longer initial holding time (at its initial temperature) leads to higher DOC light-off temperature.

With the advent of stricter vehicle emission standards, the improvement of three way catalyst performance and durability remains a pressing issue. A critical consideration in catalyst design is the potential for variations in fuel sulfur levels to have a significant impact on the ability to reach TLEV, LEV, and ULEV emission levels. As a result, a better understanding of the role of PGM composition in the interplay between thermal durability and sulfur tolerance is required. Three way catalysts representative of standard Pd-only, Pd/Rh and Pt/Rh formulations were studied over a variety of aging and evaluation conditions. The parameters investigated included aging temperature, air fuel ratio and sulfur level. Evaluations were performed on a 1994 TLEV vehicle using different sulfur level fuels. The effect of PGM loading was also included within the study.

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.

The performance characteristics of a commercial lean-NOX trap catalyst were evaluated between 200 and 500°C, using H2, CO, and a mixture of both H2 and CO as reductants before and after different high-temperature aging steps, from 600 to 750°C. Tests included NOX reduction efficiency during cycling, NOX storage capacity (NSC), oxygen storage capacity (OSC), and water-gas-shift (WGS) and NO oxidation reaction extents. The WGS reaction extent at 200 and 300°C was negatively affected by thermal degradation, but at 400 and 500°C no significant change was observed. Changes in the extent of NO oxidation did not show a consistent trend as a function of thermal degradation. The total NSC was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation but a steady decrease was observed at 350°C as the thermal degradation temperature was increased.

In a collaborative programme, the effects of gasoline sulphur content on regulated emissions from three-way catalyst equipped vehicles have been studied. The programme evaluated the sulphur tolerance of three different catalyst formulations on the same range of vehicles. The catalyst chemistries were chosen to be representative of typical current formulations in different markets, as follows: 1. Platinum/Rhodium (Pt/Rh) 2. Platinum/Rhodium/Nickel (Pt/Rh/Ni) 3. Palladium/Rhodium (Pd/Rh) Each vehicle/catalyst combination was tested with fuels containing sulphur at nominal levels of 50, 250 and 450 ppm weight. All fuels were produced using the low sulphur fuel as a base and doping to 250 and 450 ppm S with a mixture of nine sulphur compounds, typical of those actually occurring in European gasolines. The results show clear differences between the magnitudes of the sulphur effect with different catalyst formulations.

Natural gas-powered engines are widely used due to their low fuel cost and in general their lower emissions than conventional diesel engines. In order to comply with emissions regulations, an aftertreatment system is utilized to treat exhaust from natural gas engines. Stoichiometric burn natural gas engines use three-way catalyst (TWC) technology to simultaneously remove NOx, CO, and hydrocarbon (HC). Removal of methane, one of the major HC emissions from natural gas engines, is difficult due to its high stability, posing a challenge for existing TWC technologies. In this work, degreened (DG), standard bench cycle (SBC)-aged TWC catalysts and a DG Pd-based oxidation catalyst (OC) were evaluated and compared under a variety of lean/rich gas cycling conditions, simulating stoichiometric natural gas engine emissions.

Progress made in reducing engine-out particulate emissions has prompted a revival in the design of flow-through oxidation catalysts for diesel engine applications. Effort in this area has focused primarily in the area of SOF control for the further reduction of particulate emissions. The work reported here covers some of the catalyst design parameters important for SOF and gas phase pollutant control. This is illustrated with both laboratory reactor and engine evaluation data for several formulary and operating parameters. Platinum-based catalysts are shown to be generally the most active, but they require treatments or additives to reduce the inherently high activity of platinum for the oxidation of SO2 present in the exhaust. The effect of additives and their loading on the oxidation activity of Pt/alumina for HC, CO, SOF and SO2 oxidation is discussed in detail and additives are identified which reduce SO2 oxidation with minimal effect on HC, CO or SOF oxidation activity.

With increasing energy prices and concerns about the environmental impact of greenhouse gas (GHG) emissions, a growing number of national governments are putting emphasis on improving the energy efficiency of the equipment employed throughout their transportation systems. Within the U.S. transportation sector, energy use in commercial vehicles has been increasing at a faster rate than that of automobiles. A 23% increase in fuel consumption for the U.S. heavy duty truck segment is expected from 2009 to 2020. The heavy duty vehicle oil consumption is projected to grow while light duty vehicle (LDV) fuel consumption will eventually experience a decrease. By 2050, the oil consumption rate by LDVs is anticipated to decrease below 2009 levels due to CAFE standards and biofuel use. In contrast, the heavy duty oil consumption rate is anticipated to double. The increasing trend in oil consumption for heavy trucks is linked to the vitality, security, and growth of the U.S. and global economies.

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.

Cu-SSZ-13 catalysts are widely used for diesel aftertreatment applications for NOx (NO and NO2) abatement via selective catalytic reaction (SCR) due to their high conversion efficiency and excellent hydrothermal stability. Diesel engine exhaust contains small amounts of SOx due to the combustion of sulfur compounds in diesel fuel. The engine out SOx level mainly depends on the sulfur content in the diesel fuel. The presence of SOx from engine exhaust can deteriorate the SCR performance of Cu-SSZ-13 catalysts in real-world applications. This work is focused on the sulfur-induced deactivation process of a Cu-SSZ-13 catalyst under a range of simulated diesel engine operating conditions. Two catalyst deactivation modes, namely chemical poisoning and physical poisoning, are identified, primarily depending on the operating temperature. Chemical poisoning mainly results from the interaction between SOx and Cu species within the zeolite framework.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure.

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 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.

In a consortium of European industrial partners and research institutes, a combination of industrial development and scientific research was organised. The objective was to improve the catalytic NOx conversion for lean burn cars and heavy-duty trucks, taking into account boundary conditions for the fuel consumption. The project lasted for three years. During this period parallel research was conducted in research areas ranging from basic research based on a theoretical approach to full scale emission system development. NOx storage catalysts became a central part of the project. Catalysts were evaluated with respect to resistance towards sulphur poisoning. It was concluded that very low sulphur fuel is a necessity for efficient use of NOx trap technology. Additionally, attempts were made to develop methods for reactivating poisoned catalysts. Methods for short distance mixing were developed for the addition of reducing agent.

Selective NOx recirculation (SNR), involving adsorption, selective external recirculation and decomposition of the NOx by the combustion process, is itself a promising technique to abate NOx emissions. Three types of materials containing Ba: barium aluminate, barium tin perovskite and barium Y-zeolites have been developed to adsorb NOx under lean-burn or Diesel conditions, with or without the presence of S02. All these materials adsorb NO2 selectively (lean-burn conditions), and store it as nitrate/nitrite species. The desorption takes place by decomposition of these species at higher temperatures. Nitrate formation implies also sulfate formation in the presence of SO2 and SO3, while the NO2/SO2 competition governs the poisoning of such catalysts.