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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 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 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

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

Reducing Catalyst Zone Flow for Robust Emissions Performance in the Presence of Engine Air Fuel Ratio Imbalance

2017-03-28
2017-01-0961
In recent years, the EPA has implemented a requirement for monitoring the air fuel ratio balance in multi-cylinder engines such that those imbalances may not be so great as to cause the tailpipe emissions level to exceed 1.5 times the nominal emissions standard. Such imbalances may be the result of production fuel injector variation, contamination, leaks, or other malfunctions which cause the air or fuel rate to vary across the cylinders controlled by a single oxygen sensor. For many diagnostic systems that rely on the signal from the oxygen sensor, to achieve compliance to the new diagnostic standard, the sensor must see the signal from each cylinder equally. The aftertreatment system must also be robust to individual cylinder air fuel ratio variation. This paper introduces the concept of catalyst zone flow, a condition in which different cylinders of a multi-cylinder engine use different portions of the catalyst brick.
Technical Paper

Raman Studies of Automotive Catalyst Deactivation

2006-04-03
2006-01-0409
Catalyst durability is a major concern in automotive exhaust gas treatment, and can be affected by chemical and thermal history. In this work, applications of in situ UV and visible Raman spectroscopy to a variety of catalyst deactivation issues are demonstrated: a) identification and characterization of CePO4 in three-way catalysts. CePO4 forms from the interaction of phosphorus in engine oil additives with the catalyst washcoat. It affects oxygen storage and decreases catalyst conversion efficiency. b) thermal deactivation in Pd/ceria-zirconia catalysts. A compressive strain on palladium oxide as indicated by its Raman shift can serve as a diagnostic for a thermally-deactivated catalyst and thus the unavailability of the Pd for catalysis. c) sulfur poisoning, thermal deactivation and BaCO3 formation in lean NOx traps (LNT).
Technical Paper

Pre-Turbocharger Catalyst - Fast catalyst light-off evaluation

2005-05-11
2005-01-2142
Further tightened emission legislation and new engine technologies increase the requirements for the exhaust after-treatment system of modern diesel passenger cars. Especially the increasing raw emissions of HC and CO as well as the low temperature of the exhaust gas for a long period during cold start of the New European Driving Cycle (NEDC) require additional efforts in the design of the oxidation catalyst system [1]. A highly efficient micro catalyst, which is mounted in front of a turbocharger, can help to treat efficiently these high HC and CO emissions. Due to the higher temperature level in front of the turbine and the significantly increased mass and heat transfer by turbulent flow, efficiency especially during cold start is highly increased. However the packaging constraints are more critical in this area due to heat considerations and also to maintain engine performance.
Journal Article

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

2015-04-14
2015-01-1004
A laboratory study was performed to assess the potential capability of passive TWC+SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. In this system, the TWC generates the NH3 for the SCR catalyst from the feedgas NOx during rich operation. Therefore, this approach benefits from high feedgas NOx during rich operation to generate high levels of NH3 quickly and low feedgas NOx during lean operation for a low rate of NH3 consumption. It was assumed that the exhaust system needed to include a close-coupled (CC) TWC, an underbody (U/B) TWC, and an U/B SCR converter to satisfy the emission standards during 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. With a 30 s lean/10 s rich cycle and 200 ppm NO lean, 1500 ppm NO rich and the equivalent of 3.3 L of SCR volume were required to satisfy the NOx target.
Journal Article

Passive Hydrocarbon Trap to Enable SULEV-30 Tailpipe Emissions from a Flex-Fuel Vehicle on E85 Fuel

2018-04-03
2018-01-0944
Future LEV-III tailpipe (TP) emission regulations pose an enormous challenge forcing the fleet average of light-duty vehicles produced in the 2025 model year to perform at the super ultralow emission vehicle (SULEV-30) certification levels (versus less than 20% produced today). To achieve SULEV-30, regulated TP emissions of non-methane organic gas (NMOG) hydrocarbons (HCs) and oxygenates plus oxides of nitrogen (NOx) must be below a combined 30 mg/mi (18.6 mg/km) standard as measured on the federal emissions certification cycle (FTP-75). However, when flex-fuel vehicles use E85 fuel instead of gasoline, NMOG emissions at cold start are nearly doubled, before the catalytic converter is active. Passive HC traps (HCTs) are a potential solution to reduce TP NMOG emissions. The conventional HCT design was modified by changing the zeolite chemistry so as to improve HC retention coupled with more efficient combustion during the desorption phase.
Technical Paper

Oxidation and Antiwear Retention Capability of Low-Phosphorus Engine oils

2005-10-24
2005-01-3822
Future vehicle emission regulations both in the US and Europe will require maintaining catalyst efficiency for longer mileage intervals. In order to achieve this requirement, chemical restrictions are being placed on elements in engine oil that can poison catalysts. Most of phosphorus and a significant amount of sulfur in current engine oils come from zinc dialkyldithiophosphates, ZDDPs, which are a class of cost-effective multifunctional additives providing wear, oxidation and corrosion protection. Reducing ZDDP concentrations raises oxidation and wear concerns. The overall purpose of this research is to look at the antioxidation and antiwear capability of low phosphorus engine oils containing 0.05 wt% phosphorus and the potential of engine oils formulated without phosphorus. In addition to fresh oils, used oils drained from fleet vehicles were also analyzed and evaluated.
Technical Paper

Opportunities for Brazilian OBD in the Context of I/M

2008-10-07
2008-36-0168
This paper presents a comprehensive overview of Brazilian On-Board Diagnostic (OBD) regulations, Inspection and Maintenance (I/M) Programs and Aftermarket Catalyst regulations as well as an overview of similar regulations in the United States and Europe. Opportunities and technical risks are described in this context. Regulatory information contained in this Paper is intended to serve as reference only. Updated and complete rules and regulations must be used for official purposes. The implementation of the second stage of Brazilian OBD (OBDBr-2), starting in 2010, represents a significant improvement towards exhaust emission control and on-board diagnostic monitoring. Its effectiveness and credibility will be heavily influenced by how this new technology is integrated into I/M programs and how well it meshes with aftermarket catalyst regulations. Currently, Brazilian I/M regulations do not incorporate any OBD requirements and only Rio de Janeiro State has implemented an I/M Program.
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