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Ammonia/urea-SCR is a mature technology, applied worldwide for the control of NOx emissions in combustion exhausts from thermal power plants, cogeneration units, incinerators and stationary diesel engines and more recently also from mobile sources. However a greater DeNOx activity at low temperatures is desired in order to meet more and more restrictive legislations. In this paper we report transient and steady state data collected over commercial Fe-ZSM-5 and V₂O₅-WO₃/TiO₂ catalysts showing high NOx reduction efficiencies in the 200 - 350°C T-range when NO and ammonia react with nitrates, e.g., in the form of an aqueous solution of ammonium nitrate. Under such conditions a new reaction occurs, the so-called "Enhanced SCR" reaction, 2 NH₃ + 2 NO + NH₄NO₃ → 3 N₂ + 5 H₂O.

In the next years, the upcoming emission legislations are expected to introduce further restrictions on the admittable level of pollutants from vehicles measured on homologation cycles and real drive tests. In this context, the strict control of pollutant emissions at the cold start will become a crucial point to comply with the new regulation standards. This will necessarily require the implementation of novel strategies to speed-up the light-off of the reactions occurring in the after-treatment system, since the cold start conditions are the most critical one for cumulative emissions. Among the different possible technological solutions, this paper focuses on the evaluation of the potential of a burner system, which is activated before the engine start. The hypothetical burner exploits the lean combustion of an air-gasoline mixture to generate a high temperature gas stream which is directed to the catalyst section promoting a fast heating of the substrate.

Methane abatement in the exhaust gas of natural gas engines is much more challenging in respect to the oxidation of other higher order hydrocarbons. Under steady state λ sweep, the methane conversion efficiency is high at exact stoichiometric, and decreases steeply under both slightly rich and slightly lean conditions. Transient lean to rich transitions can improve methane conversion at the rich side. Previous experimental work has attributed the enhanced methane conversion to activation of methane steam reforming. The steam reforming rate, however, attenuates over time and the methane conversion rate gradually converges to the low steady state values. In this work, a reactor model is established to predict steady state and transient transition characteristics of a three-way catalyst (TWC) mounted in the exhaust of a natural gas heavy-duty engine.

Selective Catalytic Reduction (SCR) systems are nowadays widely applied for the reduction of NOx emitted from Diesel engines. The typical process is based on the injection of aqueous urea in the exhaust gases before the SCR catalyst, which determines the production of the ammonia needed for the catalytic reduction of NOx. However, this technology is affected by two main limitations: a) the evaporation of the urea water solution (UWS) requires a sufficiently high temperature of the exhaust gases and b) the formation of solid deposits during the UWS evaporation is a frequent phenomenon which compromise the correct operation of the system. In this context, to overcome these issues, a technology based on the injection of gaseous ammonia has been recently proposed: in this case, ammonia is stored at the solid state in a cartridge containing a Strontium Chloride salt and it is desorbed by means of electrical heating.

Transient and steady-state kinetic data are herein presented to analyze the inhibiting effect of ammonia on the NH₃-SCR of NO at low temperatures over a Fe-zeolite commercial catalyst for vehicles. It is shown that in SCR converter models a rate expression accounting for NH₃ inhibition of the Standard SCR reaction is needed in order to predict the specific dynamics observed both in lab-scale and in engine test bench runs upon switching on and off the ammonia feed. Two redox, dual site kinetic models are developed which ascribe such inhibition to the spill-over of ammonia from its adsorption sites, associated with the zeolite, to the redox sites, associated with the Fe promoter. Better agreement both with lab-scale intrinsic kinetic runs and with engine test-bench data, particularly during transients associated with dosing of ammonia to the SCR catalyst, is obtained assuming slow migration of NH₃ between the two sites.

The influence of adsorption and desorption processes on the non-thermal plasma enhanced catalytic reduction of NOx on NaZSM5- and Al2O3-based lean-NOx catalysts (Pt-NH4ZSM5, Cu-NaZSM5, Fe-NaZSM5, Pt-Al2O3, Pd-Al2O3, CuO-Al2O3, Ag-Al2O3) was investigated by temperature programmed reaction experiments in the temperature range from 100 °C to 600 °C. Dodecane was used as a reducing agent. Strong HC adsorption- and desorption effects were observed on the zeolite catalysts, which were not influenced by plasma-pretreatment. Adsorption of NO2 and desorption of NO occurred on Al2O3-based catalysts. By plasma-pretreatment adsorption of NO2 was induced at low temperatures. NOx-reduction rates of the catalysts Cu-NaZSM5, Fe-NaZSM5, and the Ag-Al2O3 were increased substantially by plasma-pretreatment. Both plasma-induced and catalytic oxidation of HCs were limiting factors of the NOx-reduction obtained on these catalysts.

In the last years, as a response to the more and more restrictive emission legislation, new devices (SRC, DOC, NOx-trap, DPF) have been progressively introduced as standard components of modern after-treatment system for Diesel engines. In addition, the adoption of electrical heating is nowadays regarded with interest as an effective solution to promote the light-off of the catalyst at low temperature, especially at the start-up of the engine and during the low load operation of the engine typical of the urban drive. In this work, a state-of-the-art 48 V electrical heated catalyst is considered, in order to investigate its effect in increasing the abatement efficiency of a standard DOC. The electrical heating device considered is based on a metallic support, arranged in a spiral layout, and it is heated by the Joule effect due to the passage of the electrical current.

In this paper the low temperature reduction process of nitrates stored at high temperatures over model Pt-Ba/Al2O3 LNT catalysts using both H2 and C3H6 is analyzed. The results indicate that over the Pt-Ba/Al2O3 catalyst the reduction of stored NOx with both H2 and C3H6 occurs at temperature below those corresponding to their thermal stability. Accordingly, the reduction process occurs through a Pt-catalyzed surface reaction, which does not involve, as a preliminary step, the thermal decomposition of the adsorbed NOx species. The occurrence of such a pathway also requires the co-presence of the storage element and of the noble metal on the same support.

Increasing demands on the capabilities of engine simulation and the ability to accurately predict both performance and acoustics has lead to the development of several numerical tools to help engine manufacturers during the prototyping stage. The aid of CFD tools (3D and 1D) can remarkably reduce the duration and the costs of this stage. The need of achieving good accuracy, along with acceptable computational runtime, has given the spur to the development of a geometry based quasi-3D approach. This is designed to model the acoustics and the fluid dynamics of both intake and exhaust system components used in internal combustion engines. Models of components are built using a network of quasi-3D cells based primarily on the geometry of the system. The solution procedure is based on an explicitly time marching staggered grid approach making use of a flux limiter to prevent numerical instabilities.

Prototype selective catalytic reduction (SCR) systems using urea have been demonstrated on diesel trucks in Europe in recent years. In view of upcoming stringent emissions control standards for US HD diesel engines, urea-SCR is being evaluated by US engine and truck manufacturers. The authors and their companies have worked jointly on a project to develop, test, and demonstrate urea-SCR on a US HD diesel engine and Class-8 truck. A prototype urea-SCR system was applied to a 12-liter HD diesel engine. The engine model selected is rated at 350 bhp and is common for highway trucks. The only engine modifications were changes to the injection timing control map in order to better suit the application of the urea-SCR system. This paper details two demonstration phases of the project as follows. The first phase includes recent emissions cell tests using a new compact SCR catalyst and an engine calibration optimized for lower NOX.

The potential of plasma enhanced selective catalytic reduction (PE-SCR) for Diesel-exhaust treatment at temperatures between 60 °C and 180 °C has been investigated in test bench measurements with a 1.9 liter 66 kW VW Passat TDI engine. Non-thermal plasmas were generated by pulsed electrical excitation of dielectric barrier discharge (DBD) modules each having a flow cross section of 9.5 cm2 and an electrode length of 26 cm. Monolithic V2O5-WO3/TiO2-catalysts with cell densities of 150 cpsi and 200 cpsi were used for selective catalytic reduction. First experiments were performed with a single DBD module and a catalyst volume of 3.5 liters. For temperatures between 100 °C and 160 °C and exhaust gas flow rates below 1200 liters (STP)/min NOx-reduction rates up to 14 g/h were obtained with an energy cost of about 20 Wh/g NOx. At larger gas flow rates NOx-reduction rates decreased even at higher temperatures.

This paper describes improvements achieved with regard to the long term stability and the system integrability of a previously described thick film NOx sensor for gasoline lean burn and diesel applications. (1, 2, 3) Durability test up to 1000 hours consisting of a temperature cycle have been carried out by a stoichiometric operating gasoline engine test bench. The NOx sensor demonstrates the NOx output shift in terms of the NOx sensitivity less than 5 % on a model gas apparatus and ± 7 % measuring accuracy in practical operating condition on a diesel engine after 1000 hours that is equivalent to approximately 60K miles driving. The integration of the control electronics for the sensor in its connector is achieved for the sensitive measuring current in the μA-range or less on vehicle applications. The developed electronics functions closed-loop controls for a tip temperature and oxygen pumps as well as a diagnosis of sensor malfunctions.

The accurate prediction of pollutant emissions generated by IC engines is a key aspect to guarantee the respect of the emission regulation legislation. This paper describes the approach followed by the authors to achieve a strict numerical coupling of two different 1D modeling tools in a co-simulation environment, aiming at a reliable calculation of engine-out and tailpipe emissions. The main idea is to allow an accurate 1D simulation of the unsteady flows and wave motion inside the intake and exhaust systems, without resorting to an over-simplified geometrical discretization, and to rely on advanced thermodynamic combustion models and kinetic sub-models for the calculation of cylinder-out emissions. A specific fluid dynamic approach is then used to track the chemical composition along the exhaust duct-system, in order to evaluate the conversion efficiency of after-treatment devices, such as TWC, GPF, DPF, DOC, SCR and so on.

A Euro6 gasoline light duty vehicle has been tested at the engine dynamometer and the emissions have been analyzed upstream and downstream the Three-Way-Catalyst (TWC) during a WLTC cycle. Catalyst simulations have been used for assessing the processes inside the catalytic converter using a reaction scheme based on 19 brutto reactions (direct oxidation and reduction, selective catalytic reductions with CO, C3H6 and H2, steam reforming, water-gas shift and bulk ceria as well as surface ceria reactions). The reactions have been parameterized in order to best approximate the measurements. Based on the reactions taken into account, the real vehicle emissions can be predicted with good accuracy. The simulations show that the cycle emissions comprise mainly the cold start contribution as well as discrete emission break-through events during transients. During cold start no reactions are evident in the catalyst before the temperature of the gas entering the catalyst reaches 270°C.

The transient heat transfer behavior of an automotive catalytic converter has been simulated with OpenFOAM in 1D. The model takes into consideration the gas-solid convective heat transfer, axial wall conduction and heat capacity effects in the solid phase, but also the chemical reactions of CO oxidation, based on simplified Arrhenius and Langmuir-Hinshelwood approaches. The associated parameters are the results of data in literature tuned by experiments. Simplified cases of constant flow rates and gas temperatures in the catalyst inflow have been chosen for a comprehensive analysis of the heat and mass transfer phenomena. The impact of inlet flow temperatures and inlet flow rates on the heat up characteristics as well as in the CO emissions have been quantified. A dimensional analysis is proposed and dimensionless temperature difference and space-time coordinates are introduced.

The tightening trend of regulations on the levels of admitted pollutant emissions has given a great spur to the research work in the field of combustion and after-treatment devices. Despite the improvements that can be applied to the development of the combustion process, pollutant emissions cannot be reduced to zero; for this reason, the aftertreatment system will become a key component in the path to achieving near-zero emission levels. This study focuses on the numerical analysis and optimization of different metallic substrates, specifically developed for three-way catalyst (TWC) and Diesel oxidation catalyst (DOC) applications, to improve their thermal efficiency by reducing radial thermal losses through the outer mantle. The optimization process relies on computational fluid dynamics (CFD) simulations supported by experimental measurements to validate the numerical models carried out under uncoated conditions, where chemical reactions do not occur.

NH₃/urea SCR is a very effective and widely used technology for the abatement of NOx from diesel exhaust. The SCR mechanism is well understood and the catalyst behavior can be predicted by mathematical models - as long as operation above the temperature limit for AdBlue® injection is considered. The behavior below this level is less understood. During the first seconds up to minutes after cold start, complete NOx abatement can be observed over an SCR catalyst in test bench experiments, together with a significant increase in temperature after the converter (ca. 100 K). In this work these effects have been investigated over a monolith Cu-zeolite SCR catalyst. Concentration step experiments varying NO, NO₂ and H₂O have been carried out in lab scale, starting from room temperature. Further, the interaction of C₃H₆ and CO with NOx over the SCR has been investigated.

The target of the upcoming automotive emission regulations is to promote a fast transition to near-zero emission vehicles. As such, the range of ambient and operating conditions tested in the homologation cycles is broadening. In this context, the proposed work aims to thoroughly investigate the potential of post-oxidation phenomena in reducing the light-off time of a conventional three-way catalyst. The study is carried out on a turbocharged four-cylinder gasoline engine by means of experimental and numerical activities. Post oxidation is achieved through the oxidation of unburned fuel in the exhaust line, exploiting a rich combustion and a secondary air injection dedicated strategy. The CFD methodology consists of two different approaches: the former relies on a full-engine mesh, the latter on a detailed analysis of the chemical reactions occurring in the exhaust line.

The reduction of the catalyst light-off time at the engine cold start represents a key factor for the pollutant emissions control from vehicles tested on homologation cycles and real drive conditions. The adoption of heating strategies to increase the temperature of the catalytic substrate in the early phase of the engine start is regarded as a promising solution. The present study focuses on the application of electrical heated catalyst (EHC) in an after-treatment line for a spark-ignition gasoline engine. The analysis is carried out by means of an advanced CFD framework, which includes the modeling of catalytic reactions in the substrates and accounts for the thermal evolution of all the components included in the after-treatment system.