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In order to meet recent and future stringent hydrocarbon emission regulations of passenger cars, the use of Pd-containing catalysts is of growing interest. This is especially true for Pd/Rh and Pt/Pd/Rh catalysts. To optimize the function of the individual precious metals, most high-performance catalysts have a double layer configuration. This double layer avoids undesired interactions between Pd and Rh after reacting with exhaust gas at a high temperature level. Of course, these double layer technologies lead to a more complex capacity utilization coating process during the manufacture of the catalyst. The present work summarizes the results of a research program targeting the development of a high-performance single layer Pd/Rh catalyst technology. The starting point was the functional improvement of Pd and Rh only catalysts then subsequently combining the best of these technologies.

The present paper describes the results of a joint development program focussing on a system approach to meet the proposed EURO III and IV emission standards for a passenger car equipped with a 3.2 liter, 18 valve gasoline engine. Starting with the in-production configuration of a EURO II certified vehicle (model year 1997) the following improvement points were investigated in detail. By the introduction of a close-coupled catalyst in combination with engine measures to improve the catalyst light-off the proposed EURO III limits were met. The proposed EURO IV hurdle could be overcome by further using secondary air injection during cold-start in combination with an increased precious metal loading for the close-coupled catalyst.

SOF and de-NOx catalysts are applied to heavy-duty diesel trucks which are regulated by European 13 mode or Japanese 13 mode cycles. Precious metal free catalysts can reduce SOF at low temperatures without increasing sulfates up to 670C. This catalyst shows little deterioration after 400 hours of high temperature engine aging. 32% PM and 47% SOF reduction is observed under 13 mode tests when the exhaust gas temperature exceeds 700C (ECE-13 mode). This precious metal free catalyst is suitable for diesel trucks, especially trucks with natural aspirating engine whose exhaust gas temperature is very high. De-NOx catalysts with a 300-500C NOx reduction temperature window are applied to the Japanese heavy-duty test cycle (Japan 13 mode). When secondary diesel fuel is added under modes 8 to 12, (secondary fuel addition only when catalyst inlet temperature is more than 300C), 19-25% NOx can be reduced with 2-4% fuel penalty.

The EPEFE study (European Programme on Emissions, Fuels and Engine Technologies), /1/ and other programmes have identified an increase in tailpipe NOx emissions with reduced gasoline aromatics content for modern 3-way controlled catalyst vehicles. This effect occurs with fully warmed-up catalyst under closed-loop operation. In order to understand the reasons for this effect VW and Shell have mechanistically investigated the effects of fuel properties on EMS (engine management system) and catalyst performance. Fuels with independent variation of oxygen, aromatics and mid-range volatility were tested in different VW engines. λ was monitored using sensors located both pre and post catalyst. The results confirmed that reducing gasoline aromatics content reduced engine-out emissions but increased tailpipe NOx emissions. It could be shown that differences in H/C ratio led to differences in the hydrogen content of engine-out emissions which affected the reading of the λ sensor.

Volkswagen is the first automobile manufacturer to supply a passenger car with a direct fuel injection diesel engine to the US market, starting 1996. To meet the stringent US exhaust gas legislation the very successful European 1.9 liter TDI engine has been further developed for the 1996 and 1997 Passat. This TD1 incorporates a number of innovations in advanced diesel technology. Emissions-reducing innovations include: reduced crevice volume higher injection pressures upgraded injection management integrated EGR manifold system EGR cooling diesel catalytic converter This TDI engine configuration is also to be offered in the 1997 Golf and Jetta class and the new Passat in model year 1998. Over the coming years the TDI engine concept will be further optimized by utilizing variations of the above innovations.

Zirconium dioxide (zirconia) is a well-known material often being a major component in the washcoat systems of three-way catalysts (TWC) and diesel oxidation catalysts. One important characteristic of zirconia containing washcoats is an improved aging stability which is required to meet the more and more stringent emission standards. In the last few years the utilization of zirconia became even more important - especially for high sophisticated three-way washcoat systems. This was due to the development of high temperature stable oxygen storage components, containing cerium dioxide (ceria) in combination with different other oxides - one very promising candidate being zirconia. In the present work the results of a research program are discussed, focusing on the influence of zirconia in combination with ceria and additional rare earth promoters on the stability of the oxygen storage characteristics.

Engine and laboratory tests were carried out to examine the performance of NOx adsorption catalysts for gasoline lean burn engines in fresh and aged condition. The results show that fresh NOx adsorption catalysts have the potential to meet EURO III emission standards. However, to accomplish these the fuel must contain a low sulfur concentration and the engine must be tuned to optimize the efficiency of the catalyst. After engine or furnace aging upto 750°C the catalyst shows some loss of NOx adsorption efficiency. This deterioration can be offset somewhat by increasing the frequency of lean/rich switching of the engine. Temperatures higher than 750°C may cause an irreversible destruction of the NOx, storage features while the three-way activity of the catalyst remains intact or even may improve. With reference to several physicochemical investigations it is believed that the detrimental effect of catalyst aging is attributed to two different deactivation modes.

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.

There is an increasing interest in running gasoline fueled passenger cars lean of stoichiometric air to fuel (A/F) ratio to improve fuel economy. These types of engines will operate at lean A/F ratios during cruising at partial load and return to stoichiometric or even rich conditions when more power is required. The challenge for the engine and catalyst manufacturer is to develop a system which will combine the high activity rates of a state-of-the-art three way catalyst (TWC) with the ability to reduce nitrogen oxides (NOx) under excess of oxygen. The target is to achieve the future legislation limits (EURO III/IV) in the European Union. Recent developments in automotive pollution control catalysis have shown that the utilization of NOx adsorption materials is a suitable way for reduction of NOx emissions of gasoline fueled lean burn engines.

In a joint research project between industrial companies and a number of research institutes, nitrogen oxide conversion in oxygen containing exhaust gas has been investigated according to the following procedure Basic investigations of elementary steps of the chemical reaction Production and prescreening of different catalytic material on laboratory scale Application oriented screening of industrial catalyst material Catalyst testing on a lean bum gasoline engine, passenger car diesel engines (swirl chamber and DI) and on a DI truck engine Although a number of solid body structures show nitrogen oxide reduction by hydrocarbons, only noble metal containing catalysts and transition metal exchanged zeolites gave catalytic efficiencies of industrial relevance. A maximum of 25 % NOx reduction was found in the European driving cycle for passenger cars, about 40 % for truck engines in the respective European test.

New catalysts with HC (hydrocarbon) storage ability to improve NOx conversion and to minimize fuel penalty over the US Heavy Duty Transient cycle were developed. Without secondary fuel addition, simultaneous reduction of 13% NOx and about 30% particulate was achieved by storing HC from the engine during low temperature portions of the transient cycle and releasing and using the stored HC for NOx conversion at higher temperatures. With only 1% secondary fuel addition, NOx reduction can be increased to 25%, and the particulate conversion remained relatively constant at about 20%. More than 30% NOx reduction can be obtained with 3% fuel penalty. All the pollutants (NOx, PM, HC and CO) were reduced with 0-1 % secondary fuel addition.

The spray development, combustion and emissions in a 1.9L optical, four-cylinder, direct-injection diesel engine were investigated by means of pressure analysis, high-speed cinematography, the two-colour method and exhaust gas analysis for various levels of exhaust gas recirculation (EGR), three EGR temperatures (uncontrolled, hot and cold) and three fuels (diesel, n-heptane and a two-component fuel 7D3N). Engine operating conditions included 1000 rpm/idle and 2000 rpm/2bar with EGR-rates ranging from 0 to 70%. Independent of rate, EGR was found to have a very small effect on spray angle and spray tip penetration but the auto-ignition sites seemed to increase in size and number at higher EGR-rates with associated reduction in the flame luminosity and flame temperature, by, say, 100K at 50% EGR.

The formation of soot during the first phase and the oxidation of soot during the later phase of the combustion in a direct-injection diesel engine have been investigated in detail by an extinction method. The experiments were performed in a 1.9 l near-production high-speed four-cylinder in-line direct-injection diesel engine for passenger cars for different rates of exhaust gas recirculation (EGR) and for different fuels. The measurements result in crank angle resolved and cycle-averaged soot mass concentrations in the piston bowl and the combustion chamber. The results show that with increasing EGR-rates the amount of soot formed is increased only slightly but the amount of soot oxidized during combustion decreases significantly. This is assumed to be the main reason for the increase of soot in the exhaust gas with increasing EGR-rates.

The NO formation is essentially determined by the flame temperature. In an engine the latter depends on the composition of the fuel and the intake gas. In this study the efficiency of various NO reducing measures is analysed by means of a comparison of measurements and computations for the Most frequent operation point of a 1.9 1 DI Diesel engine. The O2 concentration, which is shown to be the dominant source of influence on the flame temperature and NO formation, is varied using synthetic gas mixtures or by EGR. The molar heat capacity of CO2 and H2O in the recirculated exhaust gas, the intake temperature and the H/C ratio in the fuel are less important for the formation of NO. Measures which reduce the NO formation increase the ignition delay and thereby the fraction of the premixed combustion. The impact of EGR on the combustion process is illustrated by high speed filming.

To date, several non-SCR catalysts and catalytic systems have been suggested for NOX reduction under oxygen rich (lean) conditions, such as those which exist in diesel engine exhaust gas. However, the performance of such catalysts and catalyst systems is not clear when used on actual diesel engines. This paper reports on experimental results obtained when lean NOx catalysts are applied to diesel engine exhaust. Particularly, the catalysts' NOx performance is examined when secondary hydrocarbons are added as reducing agents directly in the exhaust gas stream. In addition, the effect of different catalyst formulations and secondary hydrocarbon addition on particulate emissions is monitored. Finally, partial system optimization is performed and the applicability of such catalysts and systems to engines operating under the US Heavy Duty Transient Cycle is examined.

This paper reports first results of research and development work to achieve Nox reduction under lean diesel exhaust gas conditions by using a special coated, zeolite based monolith catalyst. Much attention is paid to the optimization of the activated zeolite system and the influence of group Ib and VIII elements of the periodic system. A major part of the paper deals with the influence of hydrocarbons, carbon monoxide, sulfur dioxide and water on the activity of the catalyst. Another aspect discussed is the influence of the residence time of the exhaust gas components. The thermal stability and the influence of poisoning elements on the catalyst performance is demonstrated by model gas reactor tests on oven and engine aged samples. Finally, first results on the performance of the catalyst system in a vehicle dynometer test are given.

An overview is given on the state of the art of a new catalytic exhaust gas aftertreatment device for diesel engines. The function of a precious metal based, flow-through type diesel oxidation catalyst is explained. Much attention is paid to the durability of the diesel oxidation catalyst and especially to the influence of poisoning elements on the catalytic activity. Detailed data on the interaction of poisoning elements such as sulfur, zinc and phosphorus with the catalytic active sites are given. Finally it is demonstrated that it is possible to meet the stringent emission standards for diesel passenger cars in Europe with a new catalyst generation over 80.000 km AMA aging.

Several different possibilities will be described and discussed on the processes of reducing NOx in lean-burn gasoline and diesel engines. In-company studies were conducted on zeolitic catalysts. With lean-burn spark-ignition engines, hydrocarbons in the exhaust gas act as a reducing agent. In stationary conditions at λ = 1.2, NOx conversion rates of approx. 45 % were achieved. With diesel engines, the only promising variant is SCR technology using urea as a reducing agent. The remaining problems are still the low space velocity and the narrow temperature window of the catalyst. The production of reaction products and secondary reactions of urea with other components in the diesel exhaust gas are still unclarified.

Fundamental research work was undertaken to elucidate the mechanism of hydrogen sulfide formation on three-way automotive exhaust catalysts during the lean to rich engine operation sequence and to identify the role of the different catalyst components in this phenomenon. Based upon this knowledge, new catalysts were developed with reduced ability to form hydrogen sulfide by minimizing the storage of sulfur oxides. Engine dynamometer tests confirmed that the suppression of the hydrogen sulfide formation was obtained without loss of catalyst activity or aging stability. The role of the catalyst's age in the hydrogen sulfide formation is discussed. The development presented shows that it is possible to avoid “scavengers” to minimize the emission of hydrogen sulfide from three-way emission control catalysts.