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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.

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.

Global emission legislations for diesel engines are becoming increasingly stringent. While the exhaust gas composition requirements for prior iterations of emission legislation could be met with improvements in the engine's combustion process, the next issue of European, North American and Japanese emission limits greater than 2005 will require more rigorous measures, mainly employment of exhaust gas aftertreatment systems. As a result, many American diesel OEMs are considering NOx adsorbers as a means to achieve 2007+ emission standards. Since the efficacy of a NOx adsorber over its lifetime is significantly affected by sulfur (“sulfur poisoning”), forthcoming reductions in diesel fuel sulfur (down to 15 ppm), have raised industry concerns regarding compatibility and possible poisoning effects of sulfur from the lubricant.

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.

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.

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.

Changing diesel engine emission requirements for 2002 have led many diesel engine manufacturers to incorporate cooled Exhaust Gas Recirculation, EGR, as a means of reducing NOx. This has resulted in higher levels of soot being present in used oils. This paper builds on earlier work with fresh oils and describes a study of the effect of highly sooted oils on the low temperature pumpability in diesel engines. Four experimental diesel engine oils, of varying MRV TP-1 viscosities, were run in a Mack T-8 engine to obtain a soot level ranging between 6.1 and 6.6%. These sooted oils were then run in a Cummins M11 engine installed in a low temperature cell. Times to lubricate critical engine components were measured at temperatures ranging between -10 °C and -25 °C. A clear correlation was established between the MRV TP-1 viscosity of a sooted oil and the time needed to lubricate critical engine components at a given test temperature.

Production NO sensors have a strong cross-sensitivity to ammonia which limits their use for closed-loop SCR control and diagnostics since increases in sensor output can be caused by either gas component. Recently, Ammonia/NO Ratio (ANR) perturbation methods have been proposed for determining the dominant component in the post-SCR exhaust as part of the overall SCR control strategy, but these methods or the issue of sensor cross-sensitivity have not been critically evaluated or studied in their own right. In this paper the dynamic sensor direct- and cross-sensitivities are estimated from experimental FTIR data (after compensating for the dynamics of the gas sampling system) and compared to nominal values provided by the manufacturer. The ANR perturbation method and the use of different input excitations are then discussed within an analytical framework, and applied to experimental data from a large diesel engine.

Plug flow reactors, simulating engine exhaust gas, are widely used in emissions control research to gain insight into the reaction mechanisms and engineering aspects that controls activity, selectivity, and durability of catalyst components. The choice of relevant hydrocarbon (HC) species is one of the most challenging factor in such laboratory studies, given the variety of compositions that can be encountered in different application scenarios. Furthermore, this challenge is amplified by the experimental difficulties related to introducing heavier and multi-component HCs and analyzing the reaction products.

Advanced flow-reactor capabilities created at Cummins were applied to the study of the diesel particulate matter (soot) oxidation process. This approach complemented the on-engine studies with a number of important features, including accurate control of gas composition and soot layer temperature. Using the developed methodology for quantitative soot oxidation studies in a broad range of temperatures (200-700°C), an initial set of experiments was performed to compare the behavior of the real and model soot samples under the identical conditions (10%vol. of O2, 0-15%vol. of H2O). It was found that presence of H2O vapor synergistically enhances the rate of oxidation by O2 of the diesel soot sample. However, the behavior of the model soot sample (carbon black) was virtually not affected by H2O. Kinetic analysis of the obtained results revealed an unusual type of behavior, with the activation energy of soot oxidation increasing in the course of the experiment.

In August of 2011, the US Environmental Protection Agency issued new Green House Gas (GHG) emissions regulations for heavy duty vehicles. These regulations included new procedures for the evaluation of hybrid powertrains and vehicles. One of the hybrid options allows for the evaluation of an engine plus a hybrid transmission (a powertrain). For this type of testing, EPA has proposed simulating a vehicle following the hybrid vehicle test procedures, including the use of the vehicle cycles and the A to B comparison testing - as required for the full vehicle evaluation option. This paper proposes an alternative approach by defining a powertrain cycle. The powertrain cycle is based on the heavy duty engine emissions cycle - the transient FTP cycle. Simulation and test results are presented showing similar performance over the engine and vehicle cycles. This approach offers several advantages as compared to the procedure described in EPA's GHG rule.

Accumulation of lubricant and fuel derived ash in the diesel particulate filter (DPF) during vehicle operation results in a significant increase of pressure drop across the after-treatment system leading to loss of fuel economy and reduced soot storage capacity over time. Under certain operating conditions, the accumulated ash and/or soot cake layer can collapse resulting in ash deposits upstream from the typical ash plug section, henceforth termed mid-channel ash deposits. In addition, ash particles can bond (either physically or chemically) with neighboring particles resulting in formation of bridges across the channels that effectively block access to the remainder of the channel for the incoming exhaust gas stream. This phenomenon creates serious long-term durability issues for the DPF, which often must be replaced. Mid-channel deposits and ash bridges are extremely difficult to remove from the channels as they often sinter to the substrate.

Biodiesel is a promising alternative to traditional diesel fuel due to its similar combustion properties to diesel and lower carbon emissions on a well-to-wheel basis. However, combusting biodiesel still generates hydrocarbon (HC), CO, NOx and particulate matter (PM) emissions, similar to those from traditional diesel fuel usage. Therefore, aftertreatment systems will be required to reduce these emissions to meet increasingly stringent emission regulations to minimize the impact to the environment. Diesel oxidation catalysts (DOC) are widely used in modern aftertreatment systems to convert unburned HC and CO, to partially convert NO to NO2 to enhance downstream selective catalytic reaction (SCR) catalyst efficiency via fast SCR and to periodically clean-up DPF via controlled soot oxidation. In this work, we focus on the performance difference between biodiesel and diesel over a commercial DOC catalyst to identify the knowledge gap during the transition from diesel fuel to biodiesel.

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 paper will discuss the design and development of heavy-duty diesel engines to meet the US EPA 2010 on-highway standards - 0.2 g/HP-hr NOx and 0.01 g/HP-hr particulate matter (PM). In meeting these standards a combination of in-cylinder control and aftertreatment control for both NOx and particulate has been used. For NOx control, a combination of cooled exhaust gas recirculation (EGR) and selective catalytic reduction (SCR) is used. The SCR catalyst uses copper zeolite to achieve high levels of NOx conversion efficiency with minimal ammonia slip and unparalleled thermal durability. For particulate control, a diesel particulate filter (DPF) with upstream oxidation catalyst (DOC) is used. While the DPF may be actively regenerated when required, it operates predominantly with passive regeneration - enabled by the high NOx levels between the engine and the DPF, associated with high efficiency SCR systems and NO₂ production across the DOC.