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Technical Paper

Wall Permeability Estimation in Automotive Particulate Filters

2023-08-28
2023-24-0110
Porous wall permeability is one of the most critical factors for the estimation of backpressure, a key performance indicator in automotive particulate filters. Current experimental and analytical filter models could be calibrated to predict the permeability of a specific filter. However, they fail to provide a reliable estimation for the dependence of the permeability on key parameters such as wall porosity and pore size. This study presents a novel methodology for experimentally determining the permeability of filter walls. The results from four substrates with different porosities and pore sizes are compared with several popular permeability estimation methods (experimental and analytical), and their validity for this application is assessed. It is shown that none of the assessed methods predict all permeability trends for all substrates, for cold or hot flow, indicating that other wall properties besides porosity and pore size are important.
Technical Paper

Thermally Stable Pt/Rh Catalysts

1997-10-01
972909
The increasing severity in emission standards around the world has been accompanied by the development of more active, durable catalysts. With a view to investigating the effects of high thermal aging on the catalyst performance and structure, the relationships of washcoat composition, washcoat structure, and PGM location with respect to catalyst activity were clarified using a model gas test, as well as physical and chemical characterization methods. The influence of newly developed washcoat components and PGM location on catalyst performance are also demonstrated by engine bench tests. The results obtained in this study indicate the newly developed Pt/Rh catalyst techologies are appropriate for future applications in which the catalyst will be exposed to extremely high temperature and flowrates.
Technical Paper

The Use of Palladium in Advanced Catalysts

1995-02-01
950259
New advanced Pd only, Pd:Rh and Pt:Pd:Rh catalysts are compared with a current platinum rhodium catalyst after poisoning and thermal ageing. The results indicate that at equivalent precious metal cost (at 1994 prices) the advanced palladium based catalysts achieve significantly improved performance compared with current Pt, Rh and Pd technology. The new Pd:Rh formulation is recommended for close coupled locations and the Pt:Pd:Rh formulation recommended for underfloor locations where residual fuel lead may be present. The formation of H2S is shown to be low with the palladium based catalysts. Finally, it is shown that the new catalysts with balanced oxidation and reduction capability perform better in multi-brick systems than addition of a highly loaded palladium only front brick.
Technical Paper

The Impact of Fuel Sulfur Level on FTP Emissions - Effect of PGM Catalyst Type

1997-02-24
970737
With the advent of stricter vehicle emission standards, the improvement of three way catalyst performance and durability remains a pressing issue. A critical consideration in catalyst design is the potential for variations in fuel sulfur levels to have a significant impact on the ability to reach TLEV, LEV, and ULEV emission levels. As a result, a better understanding of the role of PGM composition in the interplay between thermal durability and sulfur tolerance is required. Three way catalysts representative of standard Pd-only, Pd/Rh and Pt/Rh formulations were studied over a variety of aging and evaluation conditions. The parameters investigated included aging temperature, air fuel ratio and sulfur level. Evaluations were performed on a 1994 TLEV vehicle using different sulfur level fuels. The effect of PGM loading was also included within the study.
Technical Paper

The Effects of Thermal Degradation on the Performance of a NOX Storage/Reduction Catalyst

2009-04-20
2009-01-0631
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.
Technical Paper

The Effect of Three-Way Catalyst Formulation on Sulphur Tolerance and Emissions from Gasoline Fuelled Vehicles

1994-03-01
940310
In a collaborative programme, the effects of gasoline sulphur content on regulated emissions from three-way catalyst equipped vehicles have been studied. The programme evaluated the sulphur tolerance of three different catalyst formulations on the same range of vehicles. The catalyst chemistries were chosen to be representative of typical current formulations in different markets, as follows: 1. Platinum/Rhodium (Pt/Rh) 2. Platinum/Rhodium/Nickel (Pt/Rh/Ni) 3. Palladium/Rhodium (Pd/Rh) Each vehicle/catalyst combination was tested with fuels containing sulphur at nominal levels of 50, 250 and 450 ppm weight. All fuels were produced using the low sulphur fuel as a base and doping to 250 and 450 ppm S with a mixture of nine sulphur compounds, typical of those actually occurring in European gasolines. The results show clear differences between the magnitudes of the sulphur effect with different catalyst formulations.
Technical Paper

The Design of Flow-Through Diesel Oxidation Catalysts

1993-03-01
930130
Progress made in reducing engine-out particulate emissions has prompted a revival in the design of flow-through oxidation catalysts for diesel engine applications. Effort in this area has focused primarily in the area of SOF control for the further reduction of particulate emissions. The work reported here covers some of the catalyst design parameters important for SOF and gas phase pollutant control. This is illustrated with both laboratory reactor and engine evaluation data for several formulary and operating parameters. Platinum-based catalysts are shown to be generally the most active, but they require treatments or additives to reduce the inherently high activity of platinum for the oxidation of SO2 present in the exhaust. The effect of additives and their loading on the oxidation activity of Pt/alumina for HC, CO, SOF and SO2 oxidation is discussed in detail and additives are identified which reduce SO2 oxidation with minimal effect on HC, CO or SOF oxidation activity.
Technical Paper

Research Results and Progress in LeaNOx II -A Co-operation for Lean NOx Abatement

2000-10-16
2000-01-2909
In a consortium of European industrial partners and research institutes, a combination of industrial development and scientific research was organised. The objective was to improve the catalytic NOx conversion for lean burn cars and heavy-duty trucks, taking into account boundary conditions for the fuel consumption. The project lasted for three years. During this period parallel research was conducted in research areas ranging from basic research based on a theoretical approach to full scale emission system development. NOx storage catalysts became a central part of the project. Catalysts were evaluated with respect to resistance towards sulphur poisoning. It was concluded that very low sulphur fuel is a necessity for efficient use of NOx trap technology. Additionally, attempts were made to develop methods for reactivating poisoned catalysts. Methods for short distance mixing were developed for the addition of reducing agent.
Technical Paper

Reduction of NOx in Lean Exhaust by Selective NOx-Recirculation (SNR-Technique) Part II: NOx Storage Materials

1998-10-19
982593
Selective NOx recirculation (SNR), involving adsorption, selective external recirculation and decomposition of the NOx by the combustion process, is itself a promising technique to abate NOx emissions. Three types of materials containing Ba: barium aluminate, barium tin perovskite and barium Y-zeolites have been developed to adsorb NOx under lean-burn or Diesel conditions, with or without the presence of S02. All these materials adsorb NO2 selectively (lean-burn conditions), and store it as nitrate/nitrite species. The desorption takes place by decomposition of these species at higher temperatures. Nitrate formation implies also sulfate formation in the presence of SO2 and SO3, while the NO2/SO2 competition governs the poisoning of such catalysts.
Technical Paper

Reduction of NOx in Lean Exhaust by Selective NOx-Recirculation (SNR-Technique) Part I: System and Decomposition Process

1998-10-19
982592
The SNR-technique is a new NOx aftertreatment system for lean burn gasoline and diesel applications. The objective of SNR is NOx removal from lean exhaust gas by NOx adsorption and subsequent selective external recirculation and decomposition of NOx in the combustion process. The SNR-project is composed of two major parts. Firstly the development of NOx adsorbents which are able to store large quantities of NOx in lean exhaust gas, and secondly the NOx decomposition by the combustion process. Emphasis of this paper is the investigation of NOx reduction in the combustion process, including experimental investigation and numerical simulation. The NOx decomposition process has been proven in diesel and lean-burn gasoline engines. Depending on the type of engine NOx-conversion rates up to 90 % have been observed. Regarding the complete SNR-system, including the efficiency of the adsorbing material and the NOx decomposition by the combustion, a NOx removal of more than 50% is achievable.
Technical Paper

Performance of Different Cell Structure Converters A Total Systems Perspective

1998-10-19
982634
The objective of this effort was to develop an understanding of how different converter substrate cell structures impact tailpipe emissions and pressure drop from a total systems perspective. The cell structures studied were the following: The catalyst technologies utilized were a new technology palladium only catalyst in combination with a palladium/rhodium catalyst. A 4.0-liter, 1997 Jeep Cherokee with a modified calibration was chosen as the test platform for performing the FTP test. The experimental design focused on quantifying emissions performance as a function of converter volume for the different cell structures. The results from this study demonstrate that the 93 square cell/cm2 structure has superior performance versus the 62 square cell/cm2 structure and the 46 triangle cell/cm2 structure when the converter volumes were relatively small. However, as converter volume increases the emissions differences diminish.
Technical Paper

Optimisation of Precious Metal Loadings in Automotive Catalysts Using Response Surface Methodology

1996-10-01
961907
The effect of changing catalyst precious metal ratios and loadings on close coupled catalytic converter efficiencies has been studied. The three precious metals were platinum, palladium and rhodium. The specific matrix used for the development of response surface models is a central composite design and provides the capability of visually optimising the precious metal loadings. Catalysts were evaluated using perturbed scans. lightoff curves from the dynamometer aged, and vehicle emission tests. These scans show percent conversion efficiencies of the three legislated gases; HC, CO and NOx, over a range of Air Fuel Ratios (λ). Whilst lean and rich lightoff curves provide indications of conversion efficiencies at varying temperatures. Prior to testing the catalysts were aged, using an accelerated dynamometer ageing process, to 80K simulated kilometres. The catalysts were then fitted to a vehicle and chassis roll emission tests conducted.
Technical Paper

Nickel-Free Hydrogen Sulfide Control Technology for European Applications

1993-03-01
930777
In the USA, hydrogen sulfide emissions from three-way catalytic converter-equipped automobiles are effectively suppressed by the addition of nickel to catalyst formulations. This approach is generally not utilized in catalyst formulations for Europe because of European concern about the health, safety and environmental issues surrounding the use of nickel. A modified form of iron oxide has been identified which suppresses hydrogen sulfide emissions from three-way catalysts. This suppression has been achieved without affecting the fresh or aged performance of the catalyst, a problem often encountered with other materials. The performance and durability of catalyst formulations incorporating the new material are demonstrated with a variety of aging and evaluation protocols.
Journal Article

New Methodology for Transient Engine Rig Experiments for Efficient Parameter Tuning

2013-12-20
2013-01-9043
When performing catalyst modeling and parameter tuning it is desirable that the experimental data contain both transient and stationary points and can be generated over a short period of time. Here a method of creating such concentration transients for a full scale engine rig system is presented. The paper describes a valuable approach for changing the composition of engine exhaust gas going to a DOC (or potentially any other device) by conditioning the exhaust gas with an additional upstream DOC and/or SCR. By controlling the urea injection and the DOC bypass a wide range of exhaust compositions, not possible by only controlling the engine, could be achieved. This will improve the possibilities for parameter estimation for the modeling of the DOC.
Technical Paper

Long-Term Durability of Passive Diesel Particulate Filters on Heavy-Duty Vehicles

2004-03-08
2004-01-0079
A multi-year technology validation program was completed in 2001 to evaluate ultra-low sulfur diesel fuels and passive diesel particle filters (DPF) in several different diesel fleets operating in Southern California. The fuels used throughout the validation program were diesel fuels with less than 15-ppm sulfur content. Trucks and buses were retrofitted with two types of passive DPFs. Two rounds of emissions testing were performed to determine if there was any degradation in the emissions reduction. The results demonstrated robust emissions performance for each of the DPF technologies over a one-year period. Detailed descriptions of the overall program and results have been described in previous SAE publications [2, 3, 4, 5]. In 2002, a third round of emission testing was performed by NREL on a small subset of vehicles in the Ralphs Grocery Truck fleet that demonstrated continued robust emissions performance after two years of operation and over 220,000 miles.
Technical Paper

Investigations into NOx Aftertreatment with Urea SCR for Light-Duty Diesel Vehicles

2001-09-24
2001-01-3624
Future US emissions limits are likely to mean a sophisticated nitrogen oxide (NOx) reduction technique is required for all vehicles with a diesel engine, which is likely to be either NOx trap or selective catalytic reduction (SCR) technology. To investigate the potential of SCR for NOx reduction on a light duty vehicle, a current model vehicle (EUII M1 calibration), of inertia weight 1810 kg, was equipped with an urea-based SCR injection system and non-vanadium, non-zeolitic SCR catalysts. To deal with carbon monoxide (CO), hydrocarbon (HC) and volatile organic fraction (VOF), a diesel oxidation catalyst was also incorporated into the system for most tests. Investigations into the effect of placing the oxidation catalyst at different positions in the system, changing the volume of the SCR catalysts, increasing system temperature through road load changes, varying the SCR catalyst composition, and changing the urea injection calibration are discussed.
Technical Paper

Impact of SCR Activity on Soot Regeneration and the Converse Effects of Soot Regeneration on SCR Activity on a Vanadia-SCRF®

2018-04-03
2018-01-0962
The influence of SCR (selective catalytic reduction) activity on soot regeneration was investigated using engine test measurements with and without urea dosing on a vanadia-SCRF®1, also known as a vanadia SCR coated diesel particulate filter (V.SCR-DPF). The extent and rate of passive soot regeneration is significantly reduced in the presence of SCR activity especially at high temperatures (>250 °C). The reduction in soot regeneration is because some of the NO2, which would otherwise react with the soot, is consumed by SCR reactions and consequently the rate of soot regeneration is lower when urea is dosed. The converse effects of soot oxidation on SCR activity were studied separately by analysing steady-state light-off engine measurements with different initial soot loadings on the V.SCR-DPF. The measurements show an increase in NOX conversion with increasing soot loading.
Technical Paper

Hydrocarbon Trap Technology for the Reduction of Cold-Start Hydrocarbon Emissions

1997-02-24
970741
The use of hydrocarbon traps to reduce cold-start emissions is one of the numerous methods that have been suggested to meet ULEV hydrocarbon emission requirements. To aid in our understanding of hydrocarbon traps and in the design of improved hydrocarbon trap systems, in-situ mass spectrometry has been used to speciate several hydrocarbons during the first 505 seconds of an FTP from the exhaust of a 2.0 L vehicle fitted with hydrocarbon traps in the after treatment system. This technique allows second-by-second engine-out and vehicle-out hydrocarbon speciation. The in-situ mass specrometry technique has shown that hydrocarbon traps are generally effective for trapping aromatics and C4+ alkanes and alkenes, but are ineffective in trapping methane, ethane, and ethene: Further improvements in the trapping performance for C3-C5 hydrocarbons can be made by placing a water trap in front of the hydrocarbon trap.
Technical Paper

High Performance Advanced Three-way Catalysts For The Proposed 2004 And 2008 Mercosur Emissions Standards

2000-12-01
2000-01-3303
Recently, significantly more demanding emissions standards for the Mercosur region were proposed, and the intention is that these will be introduced in 2004 and 2008. This paper describes the development of new high performance three-way catalyst formulations for conventional gasoline/gasohol fueled engines that enables them to meet these stringent standards without increasing the content of platinum group metals above the levels currently employed. The performance benefits of these advanced platinum and palladium-based catalysts are demonstrated on both engine bench and vehicles.
Technical Paper

Geometric Description of the Soot Cake in a One-Dimensional Model of an Octo-Square Asymmetric Particulate Filter

2019-04-02
2019-01-0991
Asymmetric particulate filters (PF), where the inlet channel is wider than the outlet channel, are commonly used because of their greater ash capacity. Surprisingly, very few models for asymmetric PFs have been published. This paper considers how to model the soot cake in octo-square asymmetric PFs. Some previous studies have neglected the octahedral shape of the inlet channel and instead assumed that the inlet channels were square. As the correct approach for modelling the soot cake is not obvious, three options are considered. The calculation of soot-loaded channel perimeter and hydraulic diameter (which are important for heat and mass transfer), soot thickness and backpressure as a function of soot loading are given for each geometry. In option 1, the shape of the soot-loaded channel is assumed to be geometrically similar to the soot-free channel.
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