Björn Westerberg

Model studies of NOx storage and sulphur deactivation of NOx storage catalysts

The influence of transient changes in the gas composition on the low-temperature activity of a commercial three-way catalyst and a Pt/Al2O3 model catalyst has been studied. By introducing well-controlled periodic O2 pulses to simple gas mixtures of CO or C3H6 (in N2), a substantial improvement of the low temperature oxidation activity was observed for both catalysts. The reason for low activity at low temperatures is normally attributed to self-poisoning by CO or hydrocarbons. The improved catalytic performance observed here is suggested to origin from the transients causing a surface reactant composition that is favourable for the reaction rate.The storage of NOx under lean conditions in model NOx storage catalysts as well as the deactivation by sulphur have been studied. We find that NO2 plays an important role in the storage mechanism as an oxidising agent. Two different mechanisms for this are discussed: the formation of surface peroxides and the oxidation of nitrites to nitrates, FTIR studies show that NOx is stored as surface nitrates, The sulphur deactivation is found to be more severe when SO2 is added during the rich phase than when SO2 is added during the lean period. FTIR shows the formation of bulk sulphates both under lean and rich conditions.The mechanisms for storing of NOx in platinum-barium-alumina catalysts during lean-rich transients are investigated. Oxidation of NO to NO2 is found to be an important step. NO2 is found to be important for oxidation of the catalyst or of nitrites to form nitrates. NOx is then stored in the form of surface nitrates. FTIR studies show no formation of bulk nitrates in these experiments.

The mechanism for NOx storage

The mechanisms for storing of NOx in platinum–barium–alumina catalysts during lean–rich transients are investigated. Oxidation of NO to NO2 is found to be an important step. NO2 is found to be important for oxidation of the catalyst or of nitrites to form nitrates. NOx is then stored in the form of surface nitrates. FTIR studies show no formation of bulk nitrates in these experiments.

Investigations of NOx storage catalysts

NOx storage catalysts are used to reduce nitrogen oxides from lean-burn vehicles. The nitrogen oxides are stored in the catalyst during lean conditions and subsequently released and reduced during short periods of rich conditions. In the present study, we systematically investigate the sequence of elementary steps in the NOx reduction cycle, and the extent to which these steps influence the maximum NOx, reduction potential of the catalyst. As a model system, we use barium oxide as the NOx, storing compound in a Pt/Rh/Al2O3 system. Kinetics of NO oxidation, NO and NO2 adsorption, NO and NO2 release and reduction are studied under controlled conditions with systematic variations of temperature, gas composition, and storing/release times. The transient experiments comprise a storing phase using a lean NO/C3H6/O2/N2 gas mixture, and a regenerating phase where the O2 now is turned off. Experimentally, a significant amount of NOx is found to be stored in the Ba-containing material. A maximum in NOx storage is observed around 380 degrees C. For most of the experiments, there are clear NO and NO2 desorption peaks upon switching from the storing to the regeneration phase. TPD studies of NO and NO2 reveal a significant difference between prereduced and pre-oxidised samples where the former produce predominantly N2 and N2O at around 200 degrees C while NO and O2 desorb from the latter around 500 degrees C. In situ FTIR spectra show nitrate peaks in the region 1300-1400 cm(-1) when NOx is stored under lean conditions.

Transient modelling of a HC-SCR catalyst for diesel exhaust aftertreatment

The kinetics of a catalyst for hydrocarbon-selective catalytic reduction (HC-SCR) exhaust aftertreatment has been examined by means of transient experiments on a heavy-duty diesel engine rig. The influences of temperature, NO2 concentration, and the transient injection of hydrocarbon on the conversion of NO,, CO, and hydrocarbon were studied in a systematic manner. Hydrocarbon conversion was high and NO, conversion was related to the amount of injected hydrocarbon at high temperatures. At lower temperatures hydrocarbon conversion was low and NOx conversion was not directly related to hydrocarbon injection rate. Increased exhaust NO2/NO ratio resulted in NOx conversion at lower temperatures and also in accumulation of NO., on the catalyst surface. The findings are in agreement with results from recent studies of the selective catalytic reduction of NO by propene. A catalyst model was designed in accordance to these studies and fitted to results from tailored and standard European transient cycles (ETC). The model shows reasonable agreement with experimental CO, NO, and NO2) data. Experimental hydrocarbon data are not as well reproduced, presumably due to the model approximation of hydrocarbons to one species. The full catalyst model used in the study is presented, including reaction kinetics and equations for mass and heat transfer. Mechanistic aspects are discussed and related to other studies

Sulphur dioxide deactivation of NOx storage catalysts

The influence of sulphur dioxide on the NOx storage performance of a Pt-Rh/BaO/Al2O3 model catalyst has been investigated. Addition of 2.5-25 vol.-ppm SO2 to a synthetic lean-burn exhaust, containing NO, C3H6, O2 and Ar, caused deactivation of the NOx storage function of the catalyst. The rate of deactivation was found to be proportional to the exposure of SO2. This effect is seen for temperatures between 250 and 450 degrees C. Together with in situ FTIR measurements, this leads to the conclusion that sulphur accumulates in the NOx storage component of the catalyst during the exposure. Furthermore, SO2 also inhibits the oxidation capacity of the catalyst during lean periods as is observed by a decreased NO oxidation activity. The presence of SO2 also reduces the reduction capacity of the catalyst under rich periods, which leads to an increased N2O formation and a decreased NO conversion.

A State-Space Simplified SCR Catalyst Model for Real Time Applications

The use of Selective Catalytic Reduction (SCR) is becoming increasingly more popular as a way of reducing NOx emissions from heavy duty vehicles while maintaining competitive operating costs. In order to make efficient use of these systems, it’s important to have a complete system approach when it comes to calibration of the engine and aftertreatment system. This paper presents a simplified model of a heavy duty SCR catalyst, primarily intended for use in combination with an engine-out emissions model to perform model based offline optimization of the complete system. The traditional way of modelling catalysts using a dense discretization of the catalyst channels and non-linear differential equation solvers to solve the heat and mass balance equations, requires too much computational power in this application. The presented model is also useful in other applications such as model based control. The basic model structure is a series of continuously stirred tank reactors using discretized catalyst walls to describe the mass transport in the solid phase. The simplified model uses a state-space concept. At low temperatures the model uses an implicit method of calculating the coverage differential. At higher temperatures, the model is simplified to a first order system using an operating condition dependent characteristic time constant. These simple, yet robust methods allows for long step lengths in the process of solving the differential equations. This makes the model a useful improvement over current models.

Influence of the platinum-support interaction on the direct reduction of NOx under lean conditions

Catalysts containing Pt supported on SiC, Al2O3 and ZSM-5 were prepared and studied for NOx reduction by C3H6 in Oz excess under transient (temperature ramps) and steady-state conditions. The maximum NOx reduction activity in the heating ramp experiments was similar for Pt/SiC and Pt/ZSM-5, while Pt/Al2O3 showed higher maximum activity. Both N-2 and N2O formation was observed for all catalysts, although the respective amounts varied with the investigated system. Highest Nz selectivity was observed for Pt/Al2O3. When the NOx reduction activity was studied under steady-state conditions the activity of Pt/Al2O3 decreased substantially (mainly due to a loss in N-2 production). Pt/ZSM-5 became somewhat more selective towards Na production whereas the activity and selectivity of Pt/SiC remained at about the same values as far the heating ramp experiments. Adsorbed species on the surface of the different catalysts were investigated using in-situ FTIR in order to obtain information about the reaction mechanisms. The adsorption of species on Pt/SiC was negligible, while a number of absorption bands were observed for Pt/Al2O3 (N and C containing species, and -NCO) and Pt/ZSM-5 (HC).

Model Predictive Control of a Combined EGR/SCR HD Diesel Engine

Materials Noise, Vibration and Harshness Parts and Components Power and Propulsion Quality, Reliability and Durability Safety Tests and Testing Transportation Systems Vehicles and Performance Other Options Papers by Event SAE Home > Papers> By Event> SAE 2010 World Congress & Exhibition Model Predictive Control of a Combined EGR/SCR HD Diesel Engine Date Published: 2010-04-12Paper Number: 2010-01-1175 DOI: 10.4271/2010-01-1175 Author(s): Claes Westerlund - Scania CV AB Bjorn Westerberg - Scania CV AB Ingemar Odenbrand - Lund Univ. Rolf Egnell - Lund Univ. View All CollapseAbstract Achieving upcoming HD emissions legislation, Euro VI / EPA 10, is a challenge for all engine manufacturers. A likely solution to meet the NO x limit is to use a combination of EGR and SCR. Combining these two technologies poses new challenges and possibilities when it comes to optimization and calibration.

Optimisation of a dosing strategy for an HC-SCR diesel exhaust after-treatment system

Several principal aspects and components of an advanced catalytic exhaust after-treatment system for NO, reduction on a heavy-duty diesel truck engine have been systematically examined and evaluated. The after-treatment system consists of de-NO, catalysts, injection of a reducing agent (diesel fuel), and computer programs to model the engine and catalysts in real time. These models are combined with a third program, a strategy, to control the injection of reducing agent during transient operation. Evaluation of the system was performed using the standard European transient cycle (ETC). The benefits and disadvantages of an oxidation catalyst upstream the reductant injection are clarified. Whereas an increased NO2/NO ratio is beneficial at larger reductant dosages, the effects of temperature levelling and delay are detrimental for system performance. The dynamic effect of introducing a strategy for distributing the reducing agent in time is elucidated. The strategy itself is presented and the process of its systematic optimisation is closely followed. Implications of the optimisation are that catalyst temperature is the most important variable in the strategy. Also, a considerable part of the reducing agent should be distributed at low and intermediate temperatures, for utilising an increased NO2/NO ratio. Furthermore, results suggest that a smooth, rather than instantaneous, adjustment of reductant dosage to driving conditions is necessary. Finally, a set-up with two injectors is examined for its potential in the application. It is shown to be of disadvantage for the ETC as a whole, but may not be so at lower exhaust gas flows.

Kinetic study of the selective catalytic reduction of nitric oxides with hydrocarbon in diesel exhausts

The kinetics of the selective catalytic reduction of nitric oxides (NOx) on a proprietary high temperature catalyst with diesel as the reductant have been studied. The objective was to derive a kinetic model that can be used for real time simulation of the catalyst. In the extension, the real time simulation will be used when controlling the injection of reductant. This is a requirement for achieving a high efficiency and a low fuel penalty. The response time and the NOx conversion level upon transient diesel injection was found to be dependent on the temperature. At temperatures below 570 K very low or no NOx conversion was observed. Above 570 K a small conversion was observed. No direct response upon diesel injection could be distinguished and the NOx conversion was independent on the hydrocarbon concentration. As the temperature was increased the response became apparent and then faster and the conversion level gradually became more dependent on the hydrocarbon concentration. Above 700 K the response was immediate (response time less than 15 s) and the conversion level was directly dependent on the hydrocarbon concentration. It was concluded that the NOx reduction proceeds via the formation of a hydrocarbon intermediate and the successive reaction between the hydrocarbon intermediate and NOx. When this reaction mechanism was modeled many features of the catalyst behaviour were reproduced. (Less)