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The regulations for mobile applications will become stricter in Euro 6 and further emission levels and require the use of active aftertreatment methods for NOX and particulate matter. SCR and LNT have been both used commercially for mobile NOX removal. An alternative system is based on the combination of these two technologies. Developments of catalysts and whole systems as well as final vehicle demonstrations are discussed in this study. The small and full-size catalyst development experiments resulted in PtRh/LNT with optimized noble metal loadings and Cu-SCR catalyst having a high durability and ammonia adsorption capacity. For this study, an aftertreatment system consisting of LNT plus exhaust bypass, passive SCR and engine independent reductant supply by on-board exhaust fuel reforming was developed and investigated. The concept definition considers NOX conversion, CO2 drawback and system complexity.

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.

NOx adsorbers are very sensitive to sulfur poisoning and future fuel standards are unlikely to be sufficient to prevent the system from requiring periodic desulfation procedures. The purpose of this paper is to present the effects of low fuel sulfur content such as 50 ppm and 10 ppm on the NOx adsorber efficiency for a diesel application. Through this study, the influence of the substrate cell geometry has also been assessed. The use of a 10 ppm sulfur fuel is not enough to maintain, at a high level, the NOx adsorber performance during a 40,000 km aging test. The desulfation criterion (efficiency loss of 30%) is reached after the first 16,000 km. However, the desulfation operation is not enough to recover the initial catalyst performance and the poisoning velocity increases as the catalyst ages. The hexagonal cell substrate catalyst is less sensitive to sulfur poisoning than a square cell substrate catalyst so that its desulfation frequency is much lower.

The California LEV1 II program will be introduced in the year 2003 and requires a further reduction of the exhaust emissions of passenger cars. The cold start emissions represent the main part of the total emissions of the FTP2-Cycle. Cold start emissions can be efficiently reduced by injecting secondary air (SA) in the exhaust port making compliance with the most stringent standards possible. The thermochemical conditions (mixing rate and temperature of secondary air and exhaust gas, exhaust gas composition, etc) prevailing in the exhaust system are described in this paper. This provides knowledge of the conditions for auto ignition of the mixture within the exhaust manifold. The thus established exothermal reaction (exhaust gas post-combustion) results in a shorter time to light-off temperature of the catalyst. The mechanisms of this combustion are studied at different engine idle conditions.

No efficient catalyst presently exists for deNOx in lean burn conditions. Furthermore, actual catalysts generally deactivate during reaction. A cylindrical DBD non-thermal plasma reactor was coupled with a stable three-function catalyst in order to verify the nature of the effect of the plasma on the catalytic process. A mixture of NO/O2/C3H6 in N2 was used as a lean model exhaust. The plasma was found to perform two of the three functions: NO oxidation to NO2 and propene activation through the partial oxidation of the hydrocarbon to aldehyde or alcohol. A complete catalyst containing the first two previous functions and the associative chemisorption of NO (third function) was used, as well as a simplified catalyst containing only the third function. Results suggest an advantageous plasma-catalyst coupling effect on NOx remediation in accordance with the proposed catalytic model.

For substantial reduction of fuel consumption of their vehicle fleet, Volkswagen AG has decided to develop spark-ignition engines with direct fuel injection. To launch this new engine concept with stratified lean operation mode while at the same time meeting the stringent EU IV emission standards, it was necessary to develop a suitable exhaust gas aftertreatment system. This was achieved as part of an intensive co-operation between Volkswagen AG and OMG, formerly dmc2 Degussa Metals Catalysts Cerdec AG. The paper describes the demands for exhaust gas aftertreatment due to lean burn operation. In addition the main development steps of the exhaust gas aftertreatment system for Volkswagen FSI engines and catalyst durability over vehicle lifetime are discussed. Focus is laid on the catalyst system design and coating variations. Volkswagen developed a new closed-loop emission control management system which uses NOx-sensor signals for the first time worldwide.

Meeting current exhaust emission standards requires rapid catalyst light-off. Closed-coupled catalysts are commonly used to reduce light-off time by minimizing exhaust heat loss between the engine and catalyst. However, this exhaust gas system design leads to a coupling of catalyst heating and engine operation. An engine-independent exhaust gas aftertreatment can be realized by combining a burner heated catalyst system (BHC) with an underfloor catalyst located far away from the engine. This paper describes some basic characteristics of such a BHC system and the results of fitting this system into a Volkswagen Touareg where a single catalyst was located about 1.8 m downstream of the engine. Nevertheless, it was possible to reach about 50% of the current European emission standard EU 4 without additional fuel consumption caused by the BHC system.

This paper presents an after-treatment architecture combining a close coupled NOx trap and an under floor NOx trap. Instead of simply increasing the volume of the catalyst, we propose to broaden the active temperature window by splitting the LNT along the exhaust line. In order to design this architecture, a complete 1D model of NOx trap has been developed. Validated with respect to experimental data, this model has been useful to define the two volumes of LNT, making significant savings on the test bench exploitation. However, one of the main difficulties to operate the proposed architecture is the NOx purge and sulfur poisoning management. In order to optimize the NOx and sulfur purge launches, we have developed a control strategy based on an embedded reduced LNT model. These strategies have been validated on different driving cycles, by the means of simulation and of vehicle tests using rapid prototyping tools.

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.

The emissions performance of catalytic converters under different conditions of flow distribution was investigated. Computational Fluid Dynamics methods were utilised to model the maldistribution effects of different inlet cones. The effects of maldistribution on ageing, light-off and conversion were investigated using steady state tests on an engine bench. Emission testing was also conducted on a vehicle throughout ECE and EUDC test cycles. Maldistribution was found to have a significant effect on the efficiency of the catalyst during the early stages of the ECE cycle for both fresh and aged catalysts. The effects were less significant over later stages of the ECE cycle and throughout the EUDC except NOx where maldistribution did have an effect on the conversion at higher flow rates during the later stages of the test.

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.

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.

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.

In direct-injection gasoline (GDI) engines with charge stratification, minimizing engine-out nitrogen oxide (NOx) emission is crucial since exhaust-gas aftertreatment tolerates only limited amounts of NOx. Reduced NOx production directly lowers the frequency of energy-inefficient catalyst regeneration cycles. In this paper we investigate NO formation in a realistic GDI engine. Quantitative in-cylinder measurements of NO concentrations are carried out via laser-induced fluorescence imaging with excitation of NO (A-X(0,2) band at 248 nm), and subsequent fluorescence detection at 220-240 nm. Engine modifications were kept to a minimum in order to provide results that are representative of practical operating conditions. Optical access via a sapphire ring enabled identical engine geometry as a production line engine. The engine is operated with commercial gasoline (“Super-Plus”, RON 98).

A uniform flow distribution at converter inlet is one of the fundamental requirements to meet high catalytic efficiency. Commonly used tools for optimization of the inlet flow distribution are flow measurements as well as CFD analysis. This paper puts emphasis on the experimental procedures and results. The interaction of flow measurements and CFD is outlined. The exhaust gas flow is transient, compressible and hot, making in-situ flow measurements very complex. On the other hand, to utilize the advantages of flow testing at steady-state and cold conditions the significance of these results has to be verified first. CFD analysis under different boundary conditions prove that - in a first approach - the flow situation can be regarded as a sequence of successive, steady-state situations. Using the Reynolds analogy a formula for the steady-state, cold test mass flow is derived, taking into account the cylinder displacement and the rated speed.

This presented paper deals with NOx trap sulphur poisoning and its regeneration. Sulphur poisoning has been studied with different SO2 gas concentrations under laboratory and engine test bench conditions. The sulphur poisoning studies have shown that the different NOx-traps available in the market have different behaviours toward SO2 poisoning and are all very sensitive to it. The results outline a non linear relationship of the NOx trap sulphur poisoning as a function of SO2 concentration. For instance, engine bench tests show that with a 50 and a 110ppm sulphur containing gasoline, a decrease of 50% in the NOx-trap storage capacity is respectively observed after 20 and 15 hours. With a gasoline containing 20ppm of sulphur, the same deactivation level is observed after 90 hours.

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.

Studies using a bi-fuelled (autogas/gasoline) Renault Laguna vehicle meeting °the 1996 European exhaust emission legislation has demonstrated that over the European test cycle at 25°C the LPG operated vehicle provides substantial benefits of reduced emissions compared to unleaded reference gasoline. At lower test temperatures (i.e. 5°C) even larger reduction in emissions have been observed. Lower CO (up to 95% at -5°C and 65% at 25°C), HC (90% at -5°C and 40% at 25°C) emissions and lower ozone HC reactivity have been observed and could all offer significant environmental air-quality benefits for LPG. Various autogas mixtures have been tested including 70/30, 30/70 and 49/30/21 (% mass propane / butane / propene). Results show that NOx emissions for this vehicle appear dependent on autogas composition. The two gas mixtures containing only 30% butane gave about 50% more NOx at +25°C than the 70% butane autogas mixture.