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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.

The question of whether increasing the fuel economy of light-duty natural gas fueled vehicles can improve their economic competitiveness in the U.S. market, and help the US Department of Energy meet stated goals for such vehicles is explored. Key trade-offs concerning costs, exhaust emissions and other issues are presented for a number of possible advanced engine designs. Projections of fuel economy improvements for a wide range of lean-burn engine technologies have been developed. It appears that compression ignition technologies can give the best potential fuel economy, but are less competitive for light-duty vehicles due to high engine cost. Lean-burn spark ignition technologies are more applicable to light-duty vehicles due to lower overall cost. Meeting Ultra-Low Emission Vehicle standards with efficient lean-burn natural gas engines is a key challenge.

The friction and wear characteristics of three commercially-available, electrolytic coatings for aluminum engine cylinder bores were compared to those of cast iron liners. A Ni/SiC electrocomposite, a hard anodized treatment, and a Plasma Electrolytic Oxidation (PEO) coating were investigated. ASTM standard test method G133-95, non-firing test method, for linearly reciprocating sliding wear was modified to use segments of piston rings and cylinder liners. Tests were conducted using Mr. Goodwrench™ 5W30 as a lubricant at room temperature. The normal force was 150N, the reciprocating frequency was 15Hz, the stroke length was 8mm, and the test duration was 60 minutes. Kinetic friction coefficients ranged from 0.1 to 0.22, typical of boundary lubrication. The Ni/SiC and cast iron samples exhibited the lowest friction. The wear resistance of the Ni/SiC coating was superior to that of cast iron.

Laser-induced incandescence is used to measure time-resolved diesel particulate emissions for two lean NOx trap regeneration strategies that utilize intake throttling and in-cylinder fuel enrichment. The results show that when the main injection event is increased in duration and delayed 13 crank-angle degrees, particulate emissions are very high. For a repetitive pattern of 3 seconds of rich regeneration followed by 27 seconds of NOx-trap loading, we find a monotonic increase in particulate emissions during the loading intervals that approaches twice the initial baseline particulate level after 1000 seconds. In contrast, particulate emissions during the regeneration intervals are constant throughout the test sequence.

Semi-volatile species in the exhaust can condense on the primary particulate matter (PM) forming significant secondary PM mass downstream1. We developed a new thermographic technique to measure the volatility of a particle population. The instrument is called vapor-particle separator (VPS)2. A two-parameter model was used to interpret the thermographic data3. These two parameters define volatilization potential and thermodynamic capacity of the particles. The volatization potential delineates the unique particle volatility, while the thermodynamic capacity illustrates the work required to eliminate the particles. The thermodynamic capacity is found much smaller for small particles than that for large particles.

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.

On a gasoline engine platform, homogeneous charge compression ignition (HCCI) holds the promise of improved fuel economy and greatly reduced engine-out NOx emissions, without an increase in particulate matter emissions. In this investigation, a variable compression ratio (CR) engine equipped with a throttle and intake air heating was used to test the robustness of these control parameters to accommodate a series of fuels blended from reference gasoline, straight run refinery naphtha, and ethanol. Higher compression ratios allowed for operation with higher octane fuels, but operation could not be achieved with the reference gasoline, even at the highest compression ratio. Compression ratio and intake heat could be used separately or together to modulate combustion. A lambda of 2 provided optimum fuel efficiency, even though some throttling was necessary to achieve this condition. Ethanol did not appear to assist combustion, although only two ethanol-containing fuels were evaluated.

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/γ-AI2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation.

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.

Ethanol is a very attractive fuel from an end-use perspective because it has a high chemical octane number and a high latent heat of vaporization. When an engine is optimized to take advantage of these fuel properties, both efficiency and power can be increased through higher compression ratio, direct fuel injection, higher levels of boost, and a reduced need for enrichment to mitigate knock or protect the engine and aftertreatment system from overheating. The ASTM D5798 specification for high level ethanol blends, commonly called “E85,” underwent a major revision in 2011. The minimum ethanol content was revised downward from 68 vol% to 51 vol%, which combined with the use of low octane blending streams such as natural gasoline introduces the possibility of a lower octane “E85” fuel.

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.

The partnership for advancing combustion engines (PACE) is a US Department of Energy consortium involving multiple national laboratories and includes a goal of addressing key efficiency and emission barriers in light-duty engines fueled with a market-representative E10 gasoline. A major pillar of the initiative is the generation of detailed experimental data and modeling capabilities to understand and predict cold-start behavior. Cold-start, as defined by the time between first engine crank and three-way catalyst light-off, is responsible for a large percentage of NOx, unburned hydrocarbon and particulate matter emissions in light-duty engines. Minimizing emissions during cold-start is a trade-off between achieving faster light-off of the three-way catalyst and engine out emissions during that period.

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.

It is widely recognized that future NOx and particulate matter (PM) emission targets for diesel engines cannot be met solely via advanced combustion over the full engine drive cycle. Therefore some combination of advanced combustion and aftertreatment technologies will be required. In this study, advanced combustion modes operating with a diesel particulate filter (DPF) and a lean NOx trap (LNT) catalyst were evaluated on a 1.7 liter 4-cylinder diesel engine. The combustion approaches included baseline engine operation with and without exhaust gas recirculation (EGR) and one PCCI-type (premixed charge combustion ignition) combustion mode to enable high efficiency clean combustion (HECC). Five steady-state operating conditions were evaluated. At the low load setting the exhaust temperature was too low to enable LNT regeneration and oxidation; however, HECC (low NOx) was achievable.

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.

This study investigated the effects of soybean- and coconut-derived biodiesel fuels on combustion characteristics in a 1.7-liter direct injection, common rail diesel engine. Five sets of fuels were studied: 2007 ultra low sulfur diesel (ULSD), 5% and 20% volumetric blends of soybean biodiesel with ULSD (soybean B5 and B20), and 5% and 20% volumetric blends of coconut biodiesel with ULSD (coconut B5 and B20). In conventional diesel combustion mode, particulate matter (PM) and nitrogen oxides (NOx) emissions were similar for all fuels studied except soybean B20. Soybean B20 produced the lowest PM but the highest NOx emissions. Compared with conventional diesel combustion mode, high efficiency clean combustion (HECC) mode, achieved by increased EGR and combustion phasing, significantly reduced both PM and NOx emissions for all fuels studied at the expense of higher hydrocarbon (HC) and carbon monoxide (CO) emissions and an increase in fuel consumption (less than 4%).