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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.

In one-dimensional engine simulation programs the simulation of engine performance is mostly done by parameter fitting in order to match simulations with experimental data. The extensive fitting procedure is especially needed for emissions formation - CO, HC, NO, soot - simulations. An alternative to this approach is, to calculate the emissions based on detailed kinetic models. This however demands that the in-cylinder combustion-flow interaction can be modeled accurately, and that the CPU time needed for the model is still acceptable. PDF based stochastic reactor models offer one possible solution. They usually introduce only one (time dependent) parameter - the mixing time - to model the influence of flow on the chemistry. They offer the prediction of the heat release, together with all emission formation, if the optimum mixing time is given.

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.

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.

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.

1 In this paper results obtained with different particulate matter (PM) reduction technologies are presented. Diesel oxidation catalysts (DOC) are well known as a reliable PM reduction technology which can efficiently remove the soluble organic fraction (SOF) but which has no effect on the solid particles in PM. A drawback is that in combination with high sulfur fuel, oxidation of SO2 to SO3 by the DOC can occur, resulting in an increase of PM emissions. An alternative technology that is proven to significantly reduce soot emissions comprises diesel particulate wall-flow filters. High filtration efficiencies of up to 90% and beyond are feasible. The main obstacle is the combustion of the trapped soot. As shown in this paper, the application of a catalyst coating to the filter aids the filter regeneration by lowering the balance-point temperature. The main disadvantages of wall-flow filters are an increase in back-pressure and possible plugging caused by oil-ash accumulations.

Synthetic fuels are expected to play an important role for future mobility, because they can be introduced seamlessly alongside conventional fuels without the need for new infrastructure. Thus, understanding the interaction of GTL fuels with modern engines, and aftertreatment systems, is important. The current study investigates potential benefits of GTL fuel in respect of diesel particulate filters (DPF). Experiments were conducted on a Euro 4 TDI engine, comparing the DPF response to two different fuels, normal diesel and GTL fuel. The investigation focused on the accumulation and regeneration behavior of the DPF. Results indicated that GTL fuel reduced particulate formation to such an extent that the regeneration cycle was significantly elongated, by ∼70% compared with conventional diesel. Thus, the engine could operate for this increased time before the DPF reached maximum load and regeneration was needed.

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.

The awareness concerning environmental issues and the economical need for fuel savings leads to the introduction of new, highly efficient Diesel engines for passenger cars. An engine with common rail injection system could meet this target and, with the help of an advanced diesel exhaust aftertreatment system also fulfilled the new legislative emission regulations. Besides the efficient oxidation of carbon monoxide (CO), hydrocarbons (HC) and diesel particulates, such a system also requires a moderate reduction efficiency for nitrogen oxides (NOx) under excess oxygen conditions. The present paper illustrates the further progress in catalytic NOx-reduction under excess of oxygen by hydrocarbon enrichment using the common rail injection system.

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.

This paper compares 4 different EGR systems by means of simulation in GT-Power. The demands of optimum massive EGR and fresh air rates were based on experimental results. The experimental data were used to calibrate the model and ROHR, in particular. The main aim was to investigate the influence of pumping work on engine and vehicle fuel consumption (thus CO2 production) in different EGR layouts using optimum VG turbine control. These EGR systems differ in the source of pressure drop between the exhaust and intake pipes. Firstly, the engine settings were optimized under steady operation - BSFC was minimized while taking into account both the required EGR rate and fresh air mass flow. Secondly, transient simulations (NEDC cycle) were carried out - a full engine model was used to obtain detailed information on important parameters. The study shows the necessity to use natural pressure differences or renewable pressure losses if reasonable fuel consumption is to be achieved.

To support the application and design of exhaust gas aftertreatment systems for gasoline fueled passenger cars based on hydrocarbon adsorber catalysts, a computer model was developed. This model is based on simplified, lumped kinetics for the adsorption and desorption of hydrocarbons and for the oxidation of CO and hydrocarbons. Also included in the model are convective transport of heat and mass in the gas phase, mass and heat transfer to the washcoat layer, and diffusion with reaction in the washcoat layer. The continuity equations for this model with the appropriate boundary conditions were solved for a single channel assuming adiabatic behavior. After validation of the prediction on experimental results, this model was used to perform a simple parametric study on the influence of inlet temperature,CO concentration, washcoat loading, adsorber content, and cell density on the HC emission.

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.

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.

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.

Diesel particulate mass emissions and their corresponding size distributions have been investigated on a diesel passenger car at steady state conditions using standard filters and a cascade impactor. These tests have been carried out at two different engine operating conditions (2100 rpm, 2.7 and 13.3 kW, respectively) corresponding to low and high exhaust gas temperatures. Two diesel fuels differing in their sulfur content (150 ppm and 2500 ppm S) have been used for these investigations. The particulate size distribution after diesel oxidation catalyst was found to be affected by the sulfur content of the diesel fuel and by the exhaust gas temperature. Interpretations of these results on a mechanistic basis are given. The diesel particulate emission studies have been extended to dynamic vehicle tests.

The introduction of gasoline direct injection technology into the European market will depend mainly on the availability of an effective and durable aftertreatment system, in order to reach future stringent European emission standards. NOx storage technology provides a reasonable chance of fulfilling future emission goals, but durability problems such as thermal degradation and sulfur poisoning have yet to be overcome. The present paper is dedicated to these problems, and demonstrates the progress achieved so far. The influence of different aging modes and aging severity on the NOx conversion efficiency of an advanced generation of NOx storage catalysts, is described in detail. It was found that the severity of aging at comparable catalyst bed temperatures, increases in the following order: hydrothermal aging in N2/H2O < engine aging w/o fuel cut at λ-1 < furnace aging in air < engine aging with fuel cut at λ-1.

More stringent emissions regulations, space limitations for catalytic converters in modern automotive applications, and new engine technologies constitute design challenges for today's engineers. In that context high cell density thinwall and ultrathinwall ceramic substrates have been designed into advanced catalytic converters. Whereas the majority of these substrates have a square cell geometry, a potential for further emissions improvement has been predicted for hexagonal cell structures. In order to verify these predictions, a ceramic substrate has been developed combining the features of high cell density, ultrathin cell walls, and hexagonal cell structure. Based on modeling data, the actual cell density and wall thickness of the hexagonal cell substrate will be defined. The performance of that substrate will be assessed by comparing experimental emissions results using two modern Volkswagen engines.

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.