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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.

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.

A two-dimensional numerical model describing the ammonia based SCR-process on vanadia-titania catalysts is presented. The model is able to simulate coated and extruded monoliths. For the determination of the intrinsic kinetics of the various NH3-NOx reactions, unsteady microreactor experiments were used. In order to account for the influence of transport effects the kinetics were coupled with a fully transient two-phase 1D+1D monolith channel model. The model has been validated extensively with laboratory data and engine test bench measurements. After validation the model has been applied to calculate catalyst NOx conversion maps, which were used to define catalyst sizes. Additional simulations were conducted studying the influence of cell density and NH3-dosage ratio.

A 1D+1D numerical model describing the ammonia based SCR process of NO and NO2 on vanadia-titania catalysts is presented. The model is able to simulate coated and extruded monoliths. Basing on a fundamental investigation of the catalytic processes a reaction mechanism for the NO/NO2 - NH3 reacting system is proposed and modeled. After the parameterization of the reaction mechanism the reaction kinetics have been coupled with models for heat and mass transport. Model validation has been performed with engine test bench experiments. Finally the model has been applied to study the influence of NO2 on SCR efficiency within ETC and ESC testcycles, Additional simulations have been conducted to identify the potential for catalyst volume reduction if NO2 is present in the inlet feed.

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.