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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.

An LNT + SCR diesel aftertreatment system was developed in order to meet the 2010 US HD EPA on-road, and tier 4 US HD EPA off-road emission standards. This system consists of a fuel reformer (REF), lean NOx trap (LNT), catalyzed diesel particulate filter (DPF), and selective catalytic reduction (SCR) catalyst arranged in series to reduce tailpipe nitrogen oxides (NOx) and particulate matter (PM). This system utilizes a REF to produce hydrogen (H2), carbon monoxide (CO) and heat to regenerate the LNT, desulfate the LNT, and actively regenerate the DPF. The NOx stored on the LNT is reduced by the H2 and CO generated in the REF converting it to nitrogen (N2) and ammonia (NH3). NH3, which is normally an undesired byproduct of LNT regeneration, is stored in the downstream SCR which is utilized to further reduce NOx that passes through the LNT. Engine exhaust PM is filtered and trapped by the DPF reducing the tailpipe PM emissions.

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.

Commercial vehicles require fast aftertreatment heat-up to move the SCR catalyst into the most efficient temperature range to meet upcoming NOX regulations while minimizing CO2. The focus of this paper is to identify the technology levers when used independently and also together for the purpose of NOX and CO2 reduction toward achieving 2027 emissions levels while remaining CO2 neutral or better. A series of independent levers including cylinder deactivation, LO-SCR, electric aftertreatment heating and fuel burner technologies were explored. All fell short for meeting the 2027 CARB transient emission targets when used independently. However, the combinations of two of these levers were shown to approach the goal of transient emissions with one configuration meeting the requirement. Finally, the combination of three independent levers were shown to achieve 40% margin for meeting 2027 transient NOx emissions while remaining CO2 neutral.

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.

An advanced exhaust aftertreatment system is characterized following end-of-life catalyst aging to meet final Tier 4 off-highway emission requirements. This system consists of a fuel dosing system, mixing elements, fuel reformer, lean NOx trap (LNT), diesel particulate filter (DPF), and a selective catalytic reduction (SCR) catalyst. The fuel reformer is used to generate hydrogen (H2) and carbon monoxide (CO) from injected diesel fuel. These reductants are used to regenerate and desulfate the LNT catalyst. NOx emissions are reduced using the combination of the LNT and SCR catalysts. During LNT regeneration, ammonia (NH3) is intentionally released from the LNT and stored on the downstream SCR catalyst to further reduce NOx that passed through the LNT catalyst. This paper addresses system durability as the catalysts were aged to 500 desulfation events using an off-highway diesel engine.

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.

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 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.

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.

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.

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.

This paper addresses Hardware-In-the-Loop modeling and simulation for Diesel aftertreatment controls system development. Lean NOx Trap (LNT) based aftertreatment system is an efficient way to reduce NOx emission from diesel engines. From control system perspective, the main challenge in aftertreatment system is to predict temperature at various locations and estimate the stored NOx in LNT. Accurate estimation of temperatures and NOx stored in the LNT will result in an efficient system control with less fuel penalty while still maintaining the emission requirements. The optimization of the controls will prolong the lifespan of the system by avoiding overheating the catalysts, and slow the progressive process of component aging. Under real world conditions, it is quite difficult and costly to test the performance of a such complex controller by using only vehicle tests and engine cells.