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Technical Paper

Washcoat Technology and Precious Metal Loading Study Targeting the California LEV MDV2 Standard

1996-10-01
961904
Meeting the California Medium-Duty truck emissions standards presents a significant challenge to automotive engineers due to the combination of sustained high temperature exhaust conditions, high flow rates and relatively high engine out emissions. A successful catalyst for an exhaust treatment system must be resistant to high temperature deactivation, maintain cold start performance and display high three-way conversion efficiencies under most operating conditions. This paper describes a catalyst technology and precious metal loading study targeting a California Medium-Duty truck LEV (MDV2) application. At the same time a direction is presented for optimizing toward the Federal Tier 1 standard through reduction of precious metal use. The paper identifies catalytic formulations for a twin substrate, 1.23 L medium-coupled converter. Two are used per vehicle, mounted 45 cm downstream of each manifold on a 5.7 L V8 engine.
Technical Paper

Virtual Exhaust Gas Temperature Measurement

2017-03-28
2017-01-1065
Exhaust temperature models are widely used in the automotive industry to estimate catalyst and exhaust gas temperatures and to protect the catalyst and other vehicle hardware against over-temperature conditions. Modeled exhaust temperatures rely on air, fuel, and spark measurements to make their estimate. Errors in any of these measurements can have a large impact on the accuracy of the model. Furthermore, air-fuel imbalances, air leaks, engine coolant temperature (ECT) or air charge temperature (ACT) inaccuracies, or any unforeseen source of heat entering the exhaust may have a large impact on the accuracy of the modeled estimate. Modern universal exhaust gas oxygen (UEGO) sensors have heaters with controllers to precisely regulate the oxygen sensing element temperature. These controllers are duty cycle based and supply more or less current to the heating element depending on the temperature of the surrounding exhaust gas.
Journal Article

Tier 2 Test Fuel Impact to Tier 3 Aftertreatment Systems and Calibration Countermeasures

2018-04-03
2018-01-0941
During the course of emissions and fuel economy (FE) testing, vehicles that are calibrated to meet Tier 3 emissions requirements currently must demonstrate compliance on Tier 3 E10 fuel while maintaining emissions capability with Tier 2 E0 fuel used for FE label determination. Tier 3 emissions regulations prescribe lower sulfur E10 gasoline blends for the U.S. market. Tier 3 emissions test fuels specified by EPA are required to contain 9.54 volume % ethanol and 8-11 ppm sulfur content. EPA Tier 2 E0 test fuel has no ethanol and has nominal 30 ppm sulfur content. Under Tier 3 rules, Tier 2 E0 test fuel is still used to determine FE. Tier 3 calibrations can have difficulty meeting low Tier 3 emissions targets while testing with Tier 2 E0 fuel. Research has revealed that the primary cause of the high emissions is deactivation of the aftertreatment system due to sulfur accumulation on the catalysts.
Technical Paper

Three-Way Catalyst Diagnostics and Prognostics Based on Support Vector Machines

2017-03-28
2017-01-0975
A three-way catalytic converter (TWC) is an emissions control device, used to treat the exhaust gases in a gasoline engine. The conversion efficiency of the catalyst, however, drops with age or customer usage and needs to be monitored on-line to meet the on board diagnostics (OBD II) regulations. In this work, a non-intrusive catalyst monitor is developed to diagnose the track the remaining useful life of the catalyst based on measured in-vehicle signals. Using air mass and the air-fuel ratio (A/F) at the front (upstream) and rear (downstream) of the catalyst, the catalyst oxygen storage capacity is estimated. The catalyst capacity and operating exhaust temperature are used as an input features for developing a Support Vector Machine (SVM) algorithm based classifier to identify a threshold catalyst. In addition, the distance of the data points in hyperspace from the calibrated threshold plane is used to compute the remaining useful life left.
Technical Paper

The Use of Small Engines as Surrogates for Research in Aftertreatment, Combustion, and Fuels

2006-11-13
2006-32-0035
In this research, small, single cylinder engines have been used to simulate larger engines in the areas of aftertreatment, combustion, and fuel formulation effects. The use of small engines reduces overall research cost and allows more rapid experiments to be run. Because component costs are lower, it is also possible to investigate more variations and to sacrifice components for materials characterization and for subsequent experiments. Using small engines in this way is very successful in some cases. In other cases, limitations of the engines influence the results and need to be accounted for in the experimental design and data analysis. Some of the results achieved or limitations found may be of interest to the small engine market, and this paper is offered as a summary of the authors' research in these areas. Research is being conducted in two areas. First, small engines are being used to study the rapid aging and poisoning of exhaust aftertreatment catalysts.
Technical Paper

The Roles of Phosphorus and Soot on the Deactivation of Diesel Oxidation Catalysts

2009-04-20
2009-01-0628
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.
Technical Paper

The Influence of Ammonia Slip Catalysts on Ammonia, N2O and NOX Emissions for Diesel Engines

2007-04-16
2007-01-1572
The use of urea-based selective catalytic reduction (SCR) is a promising method for achieving U.S. Tier 2 diesel emission standards for NOx. To meet the Tier 2 standards for Particulate Matter (PM), a catalyzed diesel particulate filter (CDPF) will likely be present and any ammonia (NH3) that is not consumed over an SCR catalyst would pass over the CDPF to make nitrous oxide (N2O) emissions and/or oxides of nitrogen (NOx), or exit the exhaust system as NH3. N2O is undesirable due to its high greenhouse gas potential, while NOx production from the slipped NH3 would reduce overall system NOx conversion efficiency. This paper reviews certain conditions where NH3 slip past an SCR system may be a concern, looks at what would happen to this slipped NH3 over a CDPF, and evaluates the performance of various supplier NH3 slip catalysts under varied space velocities, temperatures and concentrations of NH3 and NOx.
Technical Paper

The Effects of Aging Temperature and PGM Loading on the NOx Storage Capacity of a Lean NOx Trap

2005-04-11
2005-01-1117
A laboratory aging study was performed on samples of a lean NOx trap with platinum group metal (PGM) loadings of 0.53, 1.06, 2.12, and 3.18 g/liter. The LNT samples were aged at inlet temperatures of 650°C, 750°C, 800°C, and 850°C behind samples of a three-way catalyst that were aged on a pulse-flame combustion reactor with a Ford-proprietary durability schedule representing 80,000 km of customer use. For all aging temperatures, higher PGM loadings were beneficial for low temperature NOx performance, attributable to an increase in the oxidation of NO to NO2. Conversely, lower PGM loadings were beneficial for high temperature NOx performance after aging at 650°C and 750°C, as higher loadings promoted the decomposition of the nitrates during lean operation and thereby decreased the NOx storage capability at high temperatures. Also, higher PGM loadings increased the OSC of the trap and thereby increased the purge requirements.
Journal Article

The Effect of Spark-Plug Heat Dispersal Range and Exhaust Valve Opening Timing on Cold-Start Emissions and Cycle-to-Cycle Variability

2021-09-21
2021-01-1180
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.
Journal Article

The Effect of Hydrocarbons on the Selective Catalyzed Reduction of NOx over Low and High Temperature Catalyst Formulations

2008-04-14
2008-01-1030
Selective Catalytic Reduction of NOx is a promising technology to enable diesel engines to meet certification under Tier 2 Bin 5 emissions requirements. SCR catalysts for vehicle use are typically zeolitic materials known to store both hydrocarbons and ammonia. Ammonia storage on the zeolite has a beneficial effect on NOx conversion; hydrocarbons however, compete with ammonia for storage sites and may also block access to the interior of the zeolites where the bulk of the catalytic processes take place. This paper presents the results of laboratory studies utilizing surrogate hydrocarbon species to simulate engine-out exhaust over catalysts formulated to operate in both low (≈175-500°C) and high temperature (≈250-600°C) regimes. The effects of hydrocarbon exposure of these individual species on the SCR reaction are examined and observations are made as to necessary conditions for the recovery of SCR activity.
Technical Paper

The Effect of Different Ageing Conditions on Spatial Variations in Emissions Across the Radius of a Close-coupled After-treatment System

2005-04-11
2005-01-1095
Using local emissions measurements immediately downstream of a close-coupled catalyst, spatial variations in emissions have been analysed for close-coupled catalysts with different ageing histories. Comparison of the radial emissions profiles between a uniformly-aged (oven-aged) catalyst and two vehicle-aged parts suggests that the vehicle-aged parts have substantial variations in catalyst damage across the radius of the catalyst. The radial variations in damage were confirmed by bench reactor and post-mortem studies. The radial catalyst damage profiles inferred from engine-based evaluations of vehicle aged catalysts show broad correlation with high flow areas identified by CFD predictions and high temperature regions as measured during engine tests.
Technical Paper

The Development of Low Temperature Three-Way Catalysts for High Efficiency Gasoline Engines of the Future: Part II

2018-04-03
2018-01-0939
It is anticipated that future gasoline engines will have improved mechanical efficiency and consequently lower exhaust temperatures at low load conditions, although the exhaust temperatures at high load conditions are expected to remain the same or even increase due to the increasing use of downsized turbocharged engines. In 2014, a collaborative project was initiated at Ford Motor Company, Oak Ridge National Lab, and the University of Michigan to develop three-way catalysts with improved performance at low temperatures while maintaining the durability of current TWCs. This project is funded by the U.S. Department of Energy and is intended to show progress toward the USDRIVE target of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150 °C after high mileage aging. The testing protocols specified by the USDRIVE ACEC team for stoichiometric S-GDI engines were utilized during the evaluation of experimental catalysts at all three facilities.
Journal Article

The Development of Low Temperature Three-Way Catalysts for High Efficiency Gasoline Engines of the Future

2017-03-28
2017-01-0918
In anticipation that future gasoline engines will have improved fuel efficiency and therefore lower exhaust temperatures during low load operation, a project was initiated in 2014 to develop three-way catalysts (TWC) with improved activity at lower temperatures while maintaining the durability of current TWCs. This project is a collaboration between Ford Motor Company, Oak Ridge National Laboratory, and the University of Michigan and is funded by the U.S. Department of Energy. The ultimate goal is to show progress towards the USDRIVE goal of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150°C after high mileage aging. A reactor was set up at Ford to follow the catalyst testing protocols established by the USDRIVE ACEC tech team for evaluating catalysts for stoichiometric gasoline direct-injection (S-GDI) engines; this protocol specifies a stoichiometric blend of CO/H2, NO, C3H6, C2H4, C3H8, O2, H2O, and CO2 for the evaluations.
Journal Article

TWC+LNT/SCR Systems for Satisfying Tier 2, Bin 2 Emission Standards on Lean-Burn Gasoline Engines

2015-04-14
2015-01-1006
A laboratory study was performed to assess the potential capability of TWC+LNT/SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. It was assumed that the exhaust system would need a close-coupled (CC) TWC, an underbody (U/B) TWC, and a third U/B LNT/SCR converter to satisfy the emission standards on the FTP and US06 tests while allowing lean operation for improved fuel economy during select driving conditions. Target levels for HC, CO, and NOx during lean/rich cycling were established. Sizing studies were performed to determine the minimum LNT/SCR volume needed to satisfy the NOx target. The ability of the TWC to oxidize the HC during rich operation through steam reforming was crucial for satisfying the HC target.
Journal Article

Simulations of the Fuel Economy and Emissions of Hybrid Transit Buses over Planned Local Routes

2014-04-01
2014-01-1562
We present simulated fuel economy and emissions of city transit buses powered by conventional diesel engines and diesel-hybrid electric powertrains of varying size. Six representative city drive cycles were included in the study. In addition, we included previously published aftertreatment device models for control of CO, HC, NOx, and particulate matter (PM) emissions. Our results reveal that bus hybridization can significantly enhance fuel economy by reducing engine idling time, reducing demands for accessory loads, exploiting regenerative braking, and shifting engine operation to speeds and loads with higher fuel efficiency. Increased hybridization also tends to monotonically reduce engine-out emissions, but tailpipe (post-aftertreatment) emissions are affected by complex interactions between engine load and the transient catalyst temperatures, and the emissions results were found to depend significantly on motor size and details of each drive cycle.
Technical Paper

Selective Catalytic Reduction of Oxides of Nitrogen with Ethanol/Gasoline Blends over a Silver/Alumina Catalyst in Lean Gasoline Engine Exhaust

2015-04-14
2015-01-1008
Ethanol is a very effective reductant for nitrogen oxides (NOX) over silver/alumina (Ag/Al2O3) catalysts in lean exhaust environments. With the widespread availability of ethanol/gasoline-blended fuel in the U.S., lean gasoline engines equipped with Ag/Al2O3 catalysts have the potential to deliver higher fuel economy than stoichiometric gasoline engines and to increase biofuel utilization while meeting exhaust emissions regulations. In this work a pre-commercial 2 wt% Ag/Al2O3 catalyst was evaluated on a 2.0-liter BMW lean burn gasoline direct injection engine for the selective catalytic reduction (SCR) of NOX with ethanol/gasoline blends. The ethanol/gasoline blends were delivered via in-pipe injection upstream of the Ag/Al2O3 catalyst with the engine operating under lean conditions. A number of engine conditions were chosen to provide a range of temperatures and space velocities for evaluation of catalyst performance.
Technical Paper

Selective Catalytic Reduction of NOx Emissions from a 5.9 Liter Diesel Engine Using Ethanol as a Reductant

2003-10-27
2003-01-3244
NOx emissions from a heavy-duty diesel engine were reduced by more than 90% and 80% utilizing a full-scale ethanol-SCR system for space velocities of 21000/h and 57000/h respectively. These results were achieved for catalyst temperatures between 360 and 400°C and for C1:NOx ratios of 4-6. The SCR process appears to rapidly convert ethanol to acetaldehyde, which subsequently slipped past the catalyst at appreciable levels at a space velocity of 57000/h. Ammonia and N2O were produced during conversion; the concentrations of each were higher for the low space velocity condition. However, the concentration of N2O did not exceed 10 ppm. In contrast to other catalyst technologies, NOx reduction appeared to be enhanced by initial catalyst aging, with the presumed mechanism being sulfate accumulation within the catalyst. A concept for utilizing ethanol (distilled from an E-diesel fuel) as the SCR reductant was demonstrated.
Journal Article

Selective Catalytic Reduction for Treating the NOx Emissions from Lean-Burn Gasoline Engines: Durability Assessment

2008-04-14
2008-01-0811
A laboratory study was performed to assess the potential of using selective catalytic reduction (SCR) with NH3 to treat the NOx emissions from lean-burn gasoline engines. A primary concern was the potential for hot rich exhaust conditions on the vehicle, as such conditions could degrade the zeolite-based SCR catalysts being developed for automotive applications. Samples of an iron/zeolite formulation were aged for 34 hours behind samples of a three-way catalyst (TWC) on a pulse-flame combustion reactor using different A/F ratio schedules that exposed the catalysts to either continuously lean operation, mostly stoichiometric operation, or mostly rich operation. For each A/F ratio schedule, separate SCR samples were aged with inlet temperatures of 750°C, 800°C, or 850°C. The aged SCR samples were evaluated for NOx conversion at 25K hr-1 during lean temperature ramps with 500 ppm NO and NH3.
Technical Paper

Selective Catalytic Reduction Control with Multiple Injectors

2017-03-28
2017-01-0943
Over the past decade urea-based selective catalytic reduction (SCR) has become a leading aftertreatment solution to meet increasingly stringent Nitrogen oxide (NOx) emissions requirements in diesel powertrains. A common trend seen in modern SCR systems is the use of "split-brick" configurations where two SCR catalysts are placed in thermally distinct regions of the aftertreatment. One catalyst is close-coupled to the engine for fast light-off and another catalyst is positioned under-floor to improve performance at high space velocities. Typically, a single injector is located upstream of the first catalyst to provide the reductant necessary for efficient NOx reduction. This paper explores the potential benefit, in terms of improved NOx reduction, control of NH3 slip or reduced reductant consumption, of having independently actuated injectors in front of each catalyst.
Technical Paper

Robust SCR Design Against Environmental Impacts

2016-04-05
2016-01-0954
Significant reduction in Nitrogen Oxide (NOx) emissions will be required to meet LEV III Emissions Standards for Light Duty Diesel passenger vehicles (LDD). As such, Original Equipment Manufacturers (OEMs) are exploring all possible aftertreatment options to find the best balance between performance, robustness and cost. The primary technology adopted by OEMs in North America to achieve low NOx levels is Selective Catalytic Reduction (SCR) catalyst. The critical parameters needed for SCR to work properly are: an appropriate reductant such as ammonia (NH3) typically provided as urea, adequate operating temperatures, and optimum Nitrogen Dioxide (NO2) to NOx ratios (NO2/NOx). The NO2/NOx ratio is mostly influenced by Precious Group Metals (PGM) containing catalysts located upstream of the SCR catalyst. Different versions of zeolite based SCR technologies are available on the market today and these vary in their active metal type (iron, copper, vanadium), and/or zeolite type.
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