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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.

This review paper summarizes major and representative developments in vehicular emissions regulations and technologies from 2015. The paper starts with the key regulatory advancements in the field, including newly proposed Euro 6 type regulations for Beijing, China, and India in the 2017-20 timeframe. Europe is continuing developments towards real driving emissions (RDE) standards with the conformity factors for light-duty diesel NOx ramping down to 1.5X by 2021. The California heavy duty (HD) low-NOx regulation is advancing and may be proposed in 2017/18 for implementation in 2023+. LD (light duty) and HD engine technology continues showing marked improvements in engine efficiency. Key developments are summarized for gasoline and diesel engines to meet both the emerging criteria and greenhouse gas regulations. LD gasoline concepts are achieving 45% BTE (brake thermal efficiency or net amount of fuel energy gong to the crankshaft) and closing the gap with diesel.

This review paper summarizes major developments in vehicular emissions regulations and technologies (light-duty, heavy-duty, gasoline, diesel) in 2011. First, the paper covers the key regulatory developments in the field, including proposed criteria pollutant tightening in California; and in Europe, the newly proposed PN (particle number) regulation for direct injection gasoline engines, test cycle development, and in-use testing discussions. The proposed US LD (light-duty) greenhouse gas (GHG) regulation for 2017-25 is reviewed, as well as the finalized, first-ever, US HD (heavy-duty) GHG rule for 2014-17. The paper then gives a brief, high-level overview of key emissions developments in LD and HD engine technology, covering both gasoline and diesel. Emissions challenges include lean NOx remediation for diesel and lean-burn gasoline to meet both the emerging NOx and GHG regulations.

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.

This review paper covers major regulatory and technology developments in 2018 pertinent to tailpipe emissions of greenhouse gases and criteria pollutants. Europe has proposed ambitious reductions in CO2 limits for both light- and heavy-duty sectors. The challenge is compounded with changing measurement norms and a significant shift away from fuel efficient diesels in the light-duty (LD) space. Both incremental and step changes are being made to advance internal combustion. New studies show that in-use NOx emissions from diesels can be much lower than required by the Euro 6 regulation. Discussions have already started on Euro 7 regulations, and the leading regulatory concepts and proposed technical solutions are provided. In the heavy-duty (HD) sector, the progress is outlined in improving engine and vehicle fuel efficiency through the US Department of Energy’s (DOE’s) SuperTruck II program and other representative studies.

This review summarizes the latest developments in diesel emissions regarding regulations, engines, NOx (nitrogen oxides) control, particulate matter (PM) reductions, and hydrocarbon (HC) and CO oxidation. Regulations are advancing with proposals for PN (particle number) regulations that require diesel particulate filters (DPFs) for Euro VI in 2013-14, and SULEV (super ultra low emission vehicle) fleet average light-duty (LD) emissions likely to be proposed in California for ~2017. CO₂ regulations will also impact diesel engines and emissions, probably long into the future. Engine technology is addressing these needs. Heavy-duty (HD) research engines show 90% lower NOx at the same PM or fuel consumption levels as a reference 2007 production engine. Work is starting on HD gasoline engines with promising results. In light duty (LD), engine downsizing is progressing and deNOx is emerging as a fuel savings strategy.

The development of a plasma jet ignition system is described on a 4-cyl, 140 in3 engine. Performance was evaluated on the basis of combustion flame photographs in a single-cylinder engine at 20/1 A/F dynamometer tests on a modified 4-cyl engine, and cold start emissions, fuel economy, and drivability in a vehicle at 19/1 air fuel ratio. In addition to adjustable engine variables such as air-fuel ratio and spark advance, system electrical and mechanical parameters were varied to improve combustion of lean mixtures. As examples, the air-fuel ratio range was 16-22/1, secondary ignition current was varied from 40 to 6000 mA, and plasma jet cavity and electrode geometry were optimized. It is shown that the plasma jet produces on ignition source which penetrates the mixture ahead of the initial flame front and reduces oxides of nitrogen emission, in comparison to a conventional production combustion chamber.

With the introduction of the current EU5 standards the diesel particulate filter has become a key element in the aftertreatment of diesel passenger cars. The upcoming future emission standards target primarily a further reduction in NOx emission as well as reduced fleet average CO₂ emissions. Although the particulate filter has no direct influence on the reduction of these species, the needs of future aftertreatment systems impose additional requirements on advanced filter technologies. In this paper we are introducing two new filter products based on a new low porosity aluminum titanate family that complement the current DuraTrap® AT filter products. The new products offer the potential for an increased soot mass limit or a significant reduction in pressure drop. The enhanced performance of the new filter products is discussed and demonstrated in a large number of experimental data obtained in engine bench tests.

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.

One approach to the remediation of NOx generated under lean automotive engine conditions is its controlled storage and then periodic release and reaction under enriched conditions. This process is being considered for automotive exhaust systems that will be operated pre–dominantly lean for reasons of fuel economy. Because of the special characteristics of alkali and alkaline earth elements in the presence of NOx, they are being considered for use, in conjunction with γ–alumina–based washcoats and precious metal catalysts, as NOx catalyst coatings on cellular supports. It is known that alumino–silicates will react with alkali and alkaline earth elements to form stable ceramic phases when mixtures of the components are held in direct contact at elevated temperatures.

A production calibrated GTDI 1.6L Ford Fusion was used to demonstrate low HC, CO, NOx, PM (particulate mass), and PN (particulate number) emissions using advanced catalyst technologies with newly developed high porosity substrates and coated GPFs (gasoline particulate filters). The exhaust system consisted of 1.2 liters of TWC (three way catalyst) in the close-coupled position, and 1.6L of coated GPF in the underfloor position. The catalysts were engine-aged on a dynamometer to simulate 150K miles of road aging. Results indicate that ULEV70 emissions can be achieved at ∼$40 of PGM, while also demonstrating PM tailpipe performance far below the proposed California Air Resources Board (CARB) LEV III limit of 1 mg/mi. Along with PM and PN analysis, exhaust system backpressure is also presented with various GPF designs.

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.