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The effect of various fuel-cut agings, on a Volvo Cars 4-cylinder gasoline engine, with bimetallic three-way catalysts (TWCs) was examined. Deactivation during retardation fuel-cut (low load) and acceleration fuel-cut (high load, e.g. gearshift or traction control) was compared to aging at λ=1. Three-way catalysts were aged on an engine bench comparing two fuel-cut strategies and their impact on of the life and performance of the catalysts. In greater detail, the catalytic activity, stability and selectivity were studied. Furthermore, the catalysts were thoroughly analyzed using light-off and oxygen storage capacity measurements. The emission conversion as a function of various lambda values and loads was also determined. Fresh and 40-hour aged samples showed that the acceleration fuel-cut was the strategy that had the highest contribution towards the total deactivation of the catalyst system.

In order to achieve ultra low emission levels with three-way catalysts, an early accurate air/fuel ratio control is essential. Positioning the oxygen sensor in the first part of the substrate helps to protect the oxygen sensor from being splashed by water during cold start, so that early heating and activation becomes a less limiting factor. For emission control purpose, a position of a rear sensor in the warm part of the catalyst gives improved possibilities for oxygen buffer control during catalyst warming up conditions. This enhances balancing HC and NOx in an early phase. In addition, for OBD reasons it is possible to locate the sensor in any axial position in the catalyst, which improves design possibilities for cold start detection, even for single brick catalyst systems. The paper describes the construction of the catalyst with an integrated oxygen sensor.

Traditional approaches to pollution control have been to develop benign, non-polluting processes or to abate emissions at the tailpipe or stack before release to the atmosphere. A new technology called PremAir® Catalyst Systems1 takes a different approach and directly reduces ambient, ground level ozone. For mobile applications, the new system involves coating a heat exchange device in a vehicle, such as the radiator or air conditioning condenser. The catalyst converts ozone to oxygen as ozone-containing ambient air passes over the coated surface of the radiator. The technology is relatively simple and provides a positive benefit to the environment while being totally passive to the end user application. Volvo Car Corporation was the first automobile manufacturer to voluntarily introduce the technology on their S80 luxury sedan. Nissan Motor Corporation is also using the technology on their new Sentra CA (Clean Air) certified PZEV vehicle for California.

A NOx trap catalyst was evaluated in a light-duty diesel engine bench under steady-state speed/load conditions with alternating lean and rich exhaust streams. The NOx conversion was correlated with several engine operating and control parameters, such as speed, lean / rich timing and catalyst temperature. The NOx conversion is a result of balance between stored NOx in a lean stream and the quantity of reductant applied in a rich transient pulse. The conversion is inversely proportional to the lean / rich ratio, R, (at R< 17) and engine speed. At a given speed and lean/rich ratio, the conversion is proportional to the catalyst inlet temperature. If the temperature is too high, thermal NOx release may decrease the overall NOx conversion. With a fully regenerated NOx trap catalyst, its cumulative NOx storage, at a given trapping period (or an instantaneous NOx trapping efficiency), is proportional to engine speed.

The plasma assisted catalytic reactor (PACR) approach to lean NOx abatement is a two step process. The non-thermal plasma oxidizes the engine out NO to NO2, which is then reduced to N2 over a catalyst using a hydrocarbon reductant. Whereas it was once believed that the plasma itself directly reduces NOx to N2, it has been shown that the plasma's principle function is to oxidize NO to NO2. This is accomplished without oxidizing SO2 to SO3, resulting in lower sulfate particulate when compared to standard lean NOx catalysis using platinum or reducible oxide catalysts. We have performed reactor studies comparing the relative reducibility of NO2 and NO in a synthetic diesel exhaust using diesel fuel as the hydrocarbon reductant, with attention to time-on stream behavior and determination of NOx reversibly adsorbed on the catalyst. We find that at 200°C, 50% of the NO2 disappearance over Na-ZSM5 is attributable to reversible adsorption on the catalyst.

Methane and nitric oxide conversion was studied over a Pd-based catalyst at steady state conditions. The gas mixture contained methane (0.125 %), Nitric oxide (0.125 %), carbon monoxide (0.7 %), oxygen and argon as carrier gas. The experiments were performed in a well-stirred reactor (Berty reactor) which provided constant gas composition over the catalyst. Lambda scans from λ=1.01 to 0.99 and back performed by varying the oxygen content, revealed a hysteresis in both the methane conversion and the nitric oxide conversion. The temperature and presence of nitric oxide affected the hysteresis. Complementary experiments in a synthetic exhaust gas rig revealed a more pronounced hysteresis in the presence of carbon dioxide and water. An attempt to model the hysteresis effect as a function of the palladium and palladium-oxide transformations was made.

Recently Volvo Car Corporation introduced the new PremAir® catalyst system from Engelhard Corporation on their S80 luxury sedan and the new V70 estate wagon. In this paper, performance results of this catalyst system after long-term mileage accumulation will be presented. Urban taxi vehicles were used to test the catalyst over 110,000 miles. The rate of deactivation in long-term catalyst performance was found to be dependent on the radiator design, and was least for the radiator design with the highest total geometric surface area. Subsequently, a new catalyst version was developed in order to minimize the deactivation rate. This new catalyst has been evaluated under similar taxi driving conditions over 80,000 miles, and has shown improved durability performance.

As the automobiles move closer to the ULEV, ULEV-2 and SULEV requirements, OBD (on board diagnostic) will become a design challenge. The present OBD II designs involve the use of dual oxygen sensors to monitor the hydrocarbon performance of the catalytic converter. The aim of this study was twofold: to determine the interaction of fuel sulfur and ceria in the catalyst formulation on the performance of a Pd/Rh TWC (three-way catalyst) to elucidate the sulfur and ceria interaction on the ability of the Pd/Rh catalyst to monitor the state of the catalyst relative to hydrocarbon activity and therefore it's utility in the OBD system. Catalyst samples were aged on a spark ignited engine using a “fuel cut” engine aging cycle operated for 50 hours. Maximum catalyst temperatures during this aging cycle were 850-870°C. The effect of sulfur was determined by measuring aged catalyst performance using both indolene (∼100 ppm sulfur) and premium unleaded gasoline (∼350 ppm sulfur).

On-Board Diagnostics for emissions-related components require the monitoring of the catalytic converter performance. Currently, the dual Exhaust Gas Oxygen (EGO) sensor method is the only proven method for monitoring the catalyst performance for hydrocarbons (HC). The premise for using the dual oxygen sensor method is that a catalyst with good oxygen storage capacity (OSC) will perform better than a catalyst with lower OSC. A statistical relationship has been developed to correlate HC performance with changes in OSC. The current algorithms are susceptible to false illumination of the Malfunction Indication Light (MIL) due to: 1. The accuracy with which the diagnostic algorithm can predict a catalyst malfunction condition, and 2. The precision with which the algorithm can consistently predict a malfunction. A new algorithm has been developed that provides a significant improvement in correlation between the EGO sensor signals and hydrocarbon emissions.

A novel process for coating and assembling metal converters utilizing precoated foil as building blocks has been developed which yields a converter capable of withstanding typical industry specified hot vibration protocols. The precoating process used here results in uniform catalyst coating distributions with coating adhesion to the foil on a par with the coatings' adhesion to ceramic substrates. FTP and MVEG vehicle emission performance of this unique precoated metal converter design versus a more conventional dip-coated metal monolith (parts with the same volume, cell density, and tri-metal catalyst coating), exhibited improved catalyst emission breakthrough efficiencies with respect to HC, CO, and NOx after two different engine-aging protocols. These advantages were observed on three different test vehicles across most phases of these driving cycles.

Strategic Materials at Reaction Temperatures (SMART) is an approach used to design washcoat systems for passive 4-way emission control catalysts. Light duty diesel vehicles need to meet the European Motor Vehicle Emissions Group (MVEG) cycle or U. S. Federal test procedure (FTP 75). Emissions that are monitored include hydrocarbon (HC), nitrogen oxides (NOx), carbon monoxide (CO) and total particulate matter (TPM). Low engine-exhaust temperatures (< 200°C during city driving) and high temperatures (> 500-800°C under full load and wide-open throttle) make emission control a formidable task for the catalyst designer Gas phase HC, CO and NOx reactions must be balanced with the removal of the soluble organic fraction for the vehicle to be in compliance with regulations. The SMART approach uses model gases under typical operating conditions in the laboratory to better understand the function of individual washcoat components.

Catalytic reduction of NOx from heavy duty diesel engines via addition of reductant to the exhaust is accompanied by a substantial exotherm in the catalyst bed which does not occur, for example, in a diesel oxidation catalyst. Engine tests show that thermal management in the aftertreatment system is required for optimum reductant use and maximum NOx conversion by the low-temperature (200-300°C) catalyst NSP-5, but of less importance with the high temperature (> 350°C) Catalyst A. Understanding thermal effects is also important for reconciling test results in the near-adiabatic environment of a full-sized catalyst on an engine with the near-isothermal one of a test piece in a laboratory reactor. The effects of reductant type and concentration on NOx conversion on NSP-5 were shown to result in part from non-steady state behavior of the catalyst during steady state engine operation.

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.

Because of their relatively low particulate make, lean burn natural gas vehicles (NGV's) are a viable approach to meeting the ULEV particulate standards in urban environments where NGV's are substituted for diesel powered buses and other fleet vehicles. Our experience with oxidation catalyst technology for natural gas vehicle emissions abatement has been consistent: that palladium based catalysts maintain excellent NMHC activity and particulate reduction, but methane activity, while initially very high, decreases within the first 50 hours of operation. This paper will show that sulfur oxides at sub-ppm concentrations diminish catalyst methane activity, and that inorganic ash components from the lubricating oil (P, Zn, Ca) do not significantly contribute to the initial catalyst deactivation. Using laboratory simulations, we explore systems approaches to increasing catalyst life.

A system for stratifying recycled exhaust gas (EGR) to substantially increase dilution tolerance has been applied to a port injected four-valve gasoline engine. This system, known as Combustion Control through Vortex Stratification (CCVS), has shown greatly improved fuel consumption at a stoichiometric air/fuel ratio. Both burnrate (10-90% burn angle) and HC emissions are almost completely insensitive to EGR up to best economy EGR rate. Cycle to cycle combustion variation is also excellent with a coefficient of variation of IMEP of less than 2% at best economy EGR rate. This paper describes a research programme aimed at gaining a better understanding of the in-cylinder processes in this combustion system.

Classical approaches to pollution control have been to develop benign non-polluting processes or to abate emissions at the tailpipe or stack before emitting to the atmosphere. A new technology called PremAir™ Catalyst Systems takes a different approach and reduces the existing ground level ozone. For the automotive application, the new systems involve placing a catalytic coating on a car's radiator and air conditioner condenser. As air which contains ozone passes over the radiator and condenser, the catalyst converts the ozone into oxygen. Tests conducted on a 1991 full size passenger vehicle showed that the PremAir™ Catalyst System could convert up to 90% of the ozone passing over the radiator during a driving cycle lasting 5840 kilometers (3650 miles). The effect of ozone concentration and flow rate were determined as well as the ozone destruction rate over the coated radiator. During the 5840 kilometers of driving, the catalyst exhibited steady ozone conversion.

The desire for improved fuel economy, and lower emissions of green house gases, such as CO2, is projected to increase the demand for diesel and lean-burn gasoline engines throughout the world. Several commercial diesel oxidation catalysts (DOCs) were developed in the last 3-4 years to reduce hydrocarbon, CO, and particulates emitted from the exhaust of diesel passenger cars and trucks. To meet future U.S. and European NOx standards, it is essential to develop catalyst technology that will allow NOx reduction in addition to the other three pollutants. Two materials that attracted great attention as lean NOx catalysts are the Cu/ZSM-5 and Pt based. Cu containing ZSM-5 are active for lean-NOx reduction at temperatures above 350°C, provided sufficient hydrocarbons are present as reductants.

Close coupled catalysts represent a solution being pursued by automotive engineers to meet stringent LEV and ULEV emission standards. Close coupled systems provide fast light-off by utilizing the energy in the exhaust gas rather than energy supplied by an auxiliary source such as an electrically heated catalyst or a burner in the exhaust. Previous close coupled catalyst designs were limited by the temperature capability of the catalyst coatings. A successful close coupled catalyst technology has been developed 'that is resistant to higher temperature deactivation. This technology is able to function well at low temperature during the vehicle cold start when light-off is critical. The close coupled catalyst technology has approached ULEV emission levels after aging at 1050°C for 24 hours. This study will present experimental results for a close coupled catalyst including the selection of catalyst volume, cross sectional area and combination of catalyst technologies.

Motorcycle exhaust emission standards throughout the world are becoming more stringent. Emission control systems utilizing the catalytic converter are already in production in Taiwan for 2-stroke engine motorcycles. Catalysts designed for 2-stroke engines encounter a more severe exhaust environment than do those designed for 4-stroke engines. The two aspects of increased severity are the higher temperatures and higher stresses due to engine vibrations. Precious metal catalysts have been designed to operate in the thermal environment of 2-stroke engines and such catalysts have been successfully applied to both metal and ceramic substrates. However, until now, only the metal substrate catalysts have been utilized in motorcycle application. Ceramic based catalysts have not been considered because the mounting material that holds the catalyst substrate in place did not have enough durability to withstand the thermal/vibrational forces encountered in 2-stroke engine exhaust.

A system for stratifying recycled exhaust gas (EGR) to substantially increase dilution tolerance has been applied to a multi-cylinder port injected four-valve gasoline engine. This system, dubbed Combustion Control through Vortex Stratification (CCVS), has shown greatly improved fuel consumption at stoichiometric conditions whilst retaining ULEV compatible engine-out NOx and HC emission levels. A production feasible variable air motion system has also been assessed which enables stratification at part load with no loss of performance or refinement at full load.