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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.

The selective catalytic reduction has seen widespread adoption as the best technology to reduce the NOx emissions from internal combustion engines, particularly for Diesels. This technology uses ammonia as a reducing agent, which is obtained injecting an ammonia carrier into the exhaust gas stream. The dosing of the ammonia carrier, usually AdBlue, is the major concern during the design and engine calibration phases, since the interaction between the injected liquid and the components of the exhaust system can lead to the undesired formation of solid deposits. To avoid this, the thermal and kinematic interaction between the spray and the components of the after treatment system (ATS) must be modeled accurately. In this work, the authors developed a Conjugate Heat Transfer (CHT) framework to model the kinetic and thermal interaction among the spray, the eventual liquid layer and the pipe walls.

The injection process of urea-water solution (AdBlue) determines initial conditions for reactions and catalysis and is fundamentally responsible for optimal operation of selective catalytic reduction (SCR) systems. The spray characteristics of four, commercially available, injectors (one air-assisted and three pressure-driven with different nozzle-hole configurations) are investigated with non-intrusive measuring techniques. Injection occurred in the crossflow of a channel blowing preheated air in an exhaust duct similar configuration. The effect of several gas temperatures and flows on the spray propagation and entrainment has been extensively studied by shadow imaging. Shadow images, in addition, show that the spray of the pressure-driven injectors is only marginally affected by the gas crossflow. In contrast, the air assisted spray is strongly deflected by the gas, the effect increasing with increasing gas flow.

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 application of liquid aqueous Urea Solution (AUS) as reductant in SCR exhaust after-treatment systems is now a commonly accepted industry standard. Unfortunately, less acceptable are the associated difficulties caused by incomplete decomposition of the liquid, resulting in solid deposits which accumulate in the exhaust pipe downstream of the dosing components. The correct prediction of the spray pattern and, therefore, the spray impact on the walls is a key feature for the system optimization. A mechanical patternator, designed on the basis of CFD performance assessment, involving a Lagrangian representation of the dispersed liquid fully coupled with a 3D Eulerian description of the carrier phase, has been built and used to measure the spray mass distribution.

Aqueous Urea is a non-toxic and stable ammonia carrier and its injection and mixing represent the basis for the most common de-NOx technology for mobile applications. The reactant feed preparation process is defined by evaporation, thermolysis and hydrolysis of the liquid mixture upstream the Selective Catalytic Reduction reactor, and it is strongly dependent on the interaction between spray and gaseous flow. Low-pressure driven injectors are the common industrial standard for these applications, and their behavior in almost-ambient pressure cross flows is significantly different from any in-cylinder application. For this reason, two substantially different injectors in terms of geometry and design are experimentally studied, characterizing drop sizes and velocities through Phase Doppler Anemometry (PDA) and liquid mass spatial distribution through Shadow Imaging (SI).

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.

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.