With increasing legislative demands to remove nitrogen oxides (NOx) from automotive diesel exhaust, new catalyst systems are investigated and intensely studied in industry as well in academia. The most prevailing catalytic method of choice is the selective catalytic reduction (SCR) where non-toxic urea is used as a reductant for practical reasons. Usually urea is stored in a separate tank and once injected into the exhaust system it hydrolyses into the more aggressive reductant NH3 and CO2. 4 NH3 + 4 NO + O2 -> 4 N2 + 6 H2O (NH3-SCR reaction) In regions where vanadium is not banned cost effective V2O5/WO3/TiO2 NH3-SCR catalyst systems can be used. Vanadium based are well understood, but they do however not provide stability above ca. 550 °C for longer periods of time. In exhaust treatment systems where the temperature is either high or where high temperature excursions are experienced from e.g. regeneration of particulate filters, zeolite based catalysts are therefore today the most promising candidates as high-temperature stable and non-toxic catalysts for the NH3-SCR reaction. Among the most promising candidates are the Cu- and Fe-based zeolites. Usually Fe based zeolites show good performance in the temperature range 250-500 °C and reasonable stability, whereas Cu-based zeolites show good low-temperature activity in the 180-400 °C range. The presence of copper does however also lead to a lower stability of the catalyst material. Since the low-temperature activity is of paramount importance it is necessary to improve this behavior. Therefore the purpose of this project is to investigate: - The deactivation mechanism of copper based zeolites - The influence of the zeolite framework on stability and activity These investigations should mostly be carried out on model systems such as Cu-ZSM-5 and Cu-IM-5. Recently it was found that zeolite materials with the CHA-type structure show increased hydrothermal stability, most likely originating from the small 8-MR window openings in the structure. Part of the project should therefore also include investigations on this type and other similar structures, and therefore entail: - Synthesis, in-depth characterization and catalytic testing of Cu-SSZ-13 and Cu-SAPO-34 (both structures having the CHA-type framework) - Theoretical DFT calculations on relevant parameters found by the in-depth investigation of the afore-mentioned materials - Synthesis and testing of similar materials with 8-MR windows to elucidate the influence of the zeolite sub-structure i.e. if different ring sizes in the structure influences the catalytic performance Relevant characterization techniques include, besides conventional methods, in situ methods such as: high resolution (transmission) electron microscopy, infrared (and raman) spectroscopy together with X-ray absorption spectroscopy. These are all techniques that will complement each other to produce invaluable results. Zeolites are today applied in many and diverse applications both within automotive and environmental catalysis, but also within the petrochemical and renewable chemistry. The findings of this project are therefore also believed to contribute to a more comprehensive understanding of this class of materials, relevant to many areas of heterogeneous catalysis, and therefore have the potential, to create research and business with very high impact. / Vennestrom, PNR. (2014). Selective catalytic reduction of nitrogen oxides with ammonia over microporous zeolite catalysts [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/43217

While the car fleet becomes increasingly larger it is important to lower the amounts of pollutants from each individual diesel or gasoline engine to almost zero levels. The pollutants from these engines predominantly originate from high NOx emissions and particulates, in the case when diesel is utilized, and emissions at cold start from gasoline engines. One way of treating the high NOx levels is to introduce ammonia in the diesel exhausts and let it react with the NOx to form nitrogen gas and water, which is called SCR (Selective Catalytic Reduction). However, in order to make this system reduce NOx efficiently enough for meeting future legislations, closed loop control is required. To realize this type of system an NOx or ammonia sensor is needed. The cold start emissions from gasoline vehicles are primarily due to a high light-off time for the catalytic converter. Another reason is the inability to quickly heat the sensor used for controlling the air-to-fuel ratio in the exhausts, also called the lambda value, which is required to be in a particular range for the catalytic converter to work properly. This problem may be solved utilizing another, more robust sensor for this purpose. This thesis presents the efforts made to test the SiC-based field effect transistor (SiC-FET) sensor technology both as an ammonia sensor for SCR systems and as a cold start lambda sensor. The SiC-FET sensor has been shown to be highly sensitive to ammonia both in laboratory and engine measurements. As a lambda sensor it has proven to be both sensitive and selective, and its properties have been studied in lambda stairs both in engine exhausts and in the laboratory. The influence of metal gate restructuring on the linearity of the sensor has also been investigated. The speed of response for both sensor types has been found to be fast enough for closed loop control in each application. / <p>On the day of the public defence of the doctoral thesis, the status of article III was: in press. Report code: LiU-Tek-Lic-2003:50.</p>

<p>While the car fleet becomes increasingly larger it is important to lower the amounts of pollutants from each individual diesel or gasoline engine to almost zero levels. The pollutants from these engines predominantly originate from high NO_x emissions and particulates, in the case when diesel is utilized, and emissions at cold start from gasoline engines. One way of treating the high NO_x levels is to introduce ammonia in the diesel exhausts and let it react with the NO_x to form nitrogen gas and water, which is called SCR (Selective Catalytic Reduction). However, in order to make this system reduce NO_x efficiently enough for meeting future legislations, closed loop control is required. To realize this type of system an NO_x or ammonia sensor is needed. The cold start emissions from gasoline vehicles are primarily due to a high light-off time for the catalytic converter. Another reason is the inability to quickly heat the sensor used for controlling the air-to-fuel ratio in the exhausts, also called the lambda value, which is required to be in a particular range for the catalytic converter to work properly. This problem may be solved utilizing another, more robust sensor for this purpose.</p><p>This thesis presents the efforts made to test the SiC-based field effect transistor (SiC-FET) sensor technology both as an ammonia sensor for SCR systems and as a cold start lambda sensor. The SiC-FET sensor has been shown to be highly sensitive to ammonia both in laboratory and engine measurements. As a lambda sensor it has proven to be both sensitive and selective, and its properties have been studied in lambda stairs both in engine exhausts and in the laboratory. The influence of metal gate restructuring on the linearity of the sensor has also been investigated. The speed of response for both sensor types has been found to be fast enough for closed loop control in each application.</p> / On the day of the public defence of the doctoral thesis, the status of article III was: in press. Report code: LiU-Tek-Lic-2003:50.

The increasing size of the car fleet makes it important to find ways of lowering the amounts of pollutants from each individual diesel or gasoline engine to almost zero levels. The pollutants from these engines predominantly originate from emissions at cold start, in the case when gasoline is utilized, and high NOx emissions and particulates from diesel engines. The cold start emissions from gasoline vehicles are primarily due to a high light-off time for the catalytic converter. Another reason is the inability to quickly heat the sensor used for controlling the air-to-fuel ratio in the exhausts, also called the lambda value, which is required to be in a particular range for the catalytic converter to work properly. This problem may be solved utilizing another, more robust sensor for this purpose. One way of treating the high NOx levels from diesel engines is to introduce ammonia in the exhausts and let it react with the NOx in a special catalytic converter to form nitrogen gas and water, which is called SCR (selective catalytic reduction). However, in order to make this system reduce NOx efficiently enough for meeting future legislations, closed loop control is required. To realize this type of system an NOx or ammonia sensor is needed. This thesis presents the efforts made to test the SiC-based field effect sensor device both as a cold start lambda sensor for gasoline engines and as an NH3 sensor for SCR systems in diesel engines. The MISiC (metal insulator silicon carbide) lambda sensor has proven to be both sensitive and selective to lambda, and its properties have been studied in lambda stairs both in gasoline engine exhausts and in the laboratory. There is, however, a small cross-sensitivity to CO. The influence of metal gate restructuring on the linearity of the sensor has also been investigated. The metal tends to form islands by time, which decreases the catalytic activity and thereby gives the sensor, which is binary when fresh, a linear behavior. Successful attempts to prevent the restructuring through depositing a protective layer of insulator on top of the metal were made. The influence of increasing the catalytic activity in the measurement cell was also studied. It was concluded that the location of the binary switch point of MISiC lambda sensors could be moved towards the stoichiometric value if the consumption of gases in the measurement cell was increased. The MISiC NH3 sensor for SCR systems has been shown to be highly sensitive to ammonia both in laboratory and diesel engine measurements. The influence of other diesel exhaust gas components, such as NOx, water or N2O has been found to be low. In order to make the ammonia sensor more long-term stable experiments on samples with different types of co-sputtered Pt or Ir/SiO2 gas-sensitive layers were performed. These samples turned out to be sensitive to NH3 even though they were dense and NH3 detection normally requires porous films. The speed of response for both sensor types has been found to be fast enough for closed loop control in each application. / On the day of the ublic defence of the doctoral thesis, the status of article IV was: accepted, article V was: submitted and article VII was: manuscript.

The stringent regulations of emission levels from heavy duty vehicles create a demand for new methods for reducing harmful emissions from diesel engines. This thesis deals with the modelling of the nitrogen oxide (NOx) emissions from heavy duty vehicles using a selective catalyst as an aftertreatment system, utilising ammonia (NH3) for its reduction. The process of the selective catalytic reduction (SCR) is nonlinear, since the result of the chemical reactions involved depends on the load operating point and the temperature. The purpose of this thesis is to investigate different methods for nonlinear system identification of SCR systems with control applications in mind. The main focus of the thesis is on finding suitable techniques for effective NOx reduction without the need of over dosage of ammonia. By using data collected from a simulator together with real measured data, new black-box identification techniques are developed. Scaling and convergence properties of the proposed algorithms are analysed theoretically. Some of the resulting models are used for controller development using e.g. feedback linearisation techniques, followed by validation in a simulator environment. The benefits of nonlinear modelling and control of the SCR system are highlighted in a comparison with control based on linear models of the system. Further, a multiple model approach is investigated for simultaneous control of NOx and tailpipe ammonia. The results indicate an improvement in terms of ammonia slip reduction in comparison with models that do not take the ammonia slip into account. Another approach to NOx reduction is achieved by controlling the SCR temperature using techniques developed for LPV systems. The results indicate a reduction of the accumulated NOx.

Ces travaux de thèse ont porté sur l'étude approfondie de catalyseurs à base d'argent et d'or dans la réduction catalytique sélective des NOx par C3H6. Pour le système Ag/Al2O3, nous avons réussi à fournir une explication rationnelle de l'origine de l'existence d'un optimum d'activité pour une teneur en Ag de l'ordre de 2 %pds reporté à plusieurs reprises. La caractérisation par NOx-TPD des catalyseurs Ag/Al2O3 a permis d'attribuer l'origine de cet optimum à la teneur maximale en Ag pour laquelle la dispersion quasi-atomique de l'argent est préservée. Nous avons aussi démontré pour la première fois que l'activité des catalyseurs Ag/Al2O3 dans la réduction des NOx par C3H6 en présence de H2 augmentait lorsque la densité surfacique en Ag diminuait. Ceci a été expliqué par l'augmentation du nombre de sites du support pouvant adsorber les NOx lorsque la teneur en Ag diminue. Le système catalytique Au/Al2O3 a été également étudié. En diminuant le nombre de sites d'or dans le réacteur, un effet promoteur de H2 a été mis en évidence pour la première fois pour ce système dans la réduction des NOx par C3H6. Cet effet promoteur était plus important lorsque la teneur en Au diminue. L'activité catalytique du système Au/Al2O3 a été optimisée par la cérine, le catalyseur présentant 1%pds en CeO2 et 0,5%pds en Au a montré la meilleure conversion des NOx. L'activité catalytique d'un système Au-Ag/Al2O3 a également été examinée mais trouvée moins intéressante que celles des systèmes monométalliques. La conversion des NOx en N2 en présence de H2 sur un catalyseur Ag/Al2O3 a pu être améliorée de prés de 30 % en déposant l'argent sur un support prétraité hydrothermalement. / This work provides further insights into C3H6-SCR on alumina supported silver and gold catalysts. The origin of the optimum loading of 2 wt% of Ag on Al2O3 in the C3H6-SCR of NOx was elucidated with the help of an original characterization method (NOx-TPD). The optimum loading was attributed to the maximum loading of silver on Al2O3 for which highly dispersed Ag species are preserved. Our study highlights for the first time that the H2-C3H6-SCR catalytic performance of Ag/Al2O3 samples improved in the 150-550 °C temperature domain as the Ag loading decreased well below 2 wt%. A detailed kinetic study of H2-C3H6-SCR was performed and led us to conclude that the unexpected higher catalytic performance of the Ag samples with the lower Ag surface densities was attributed to the higher concentration of active sites on the Al2O3 supporting oxide able to chemisorb NOx species. Regarding Au/Al2O3 catalysts, our work provides the first experimental evidence of an H2 effect in C3H6-SCR over Au/Al2O3 catalysts. This effect could only be observed when the number of Au catalytic sites in the reactor was decreased. The influence of the Au loading on the H2-C3H6-SCR was investigated. Au/CeO2-Al2O3 system was optimized with addition of ceria. Among the Au/CeO2-Al2O3 catalysts evaluated, the sample containing 0.5 wt% Au and 1 wt% CeO2 exhibited the best NOx conversion in C3H6-SCR at low temperature (from 150 °C). The catalytic activity of bimetallic Au-Ag /Al2O3 catalysts was investigated in C3H6-SCR and H2-C3H6-SCR. Finally, NOx conversion to N2 on Ag/Al2O3 in H2-C3H6-SCR could be improved substantially by nearly 30 % when silver is added on hydrothermally pretreated Al2O3 support.

This Master´s thesis deals with the verification calculation of boiler which burns brown coal for the application of the selective catalytic reduction method. The thesis is divided into several parts. In the first of all is performed the calculation of the furnace chamber which involves stoichiometrics calculations and enthalpy calculations of air and flue gas. In the second part the heat balance of the boiler, the boiler losses and the thermal efficiency are determined. After all the heating surfaces are calculed for the verify the dimensions. In the conclusion of the thesis we looked for the temperature range which is used for the SCR application. Then the improvements for the appropriate temperature range are designed.

My master´s thesis deals with the problems of NOx abatement that are included in flue gas. The accent is put on flue gases treatment throug cloth filter or ceramic candles, where the deposited catalyst enables NOx reduction throug the method of selective cytalytic reduction. In thesis is also describe experimental unit which current remove gaseous pollutants (dioxin, VOC and NOX) and ash on catalytic cloth filter or catalytic ceramic candles. For experimental unit has been calculated pressure drop. Pressure drop has been calculated for nominal and maximal conditions for cloth filter and ceramic candle. Last part of thesis deals with compile a experimental schemes for different concentration of NO, flow and temperature of combustion.

This thesis deals with the reduction of oxides of nitrogen (NOx) which are part of the exhaust gas combustion devices. The focus is on reduction of NOx by selective catalytic reduction (SCR) and catalyst filtration. The first part of this work deals with the formation of NOx, their hazards and related legislation. The following is an overview of the available technologies to reduce NOx in the flue gas and comparison of this methods. The following section describes the experimental catalytic filtration unit INTEQ II, where the first real experiment selective catalytic reduction of NOx with ammonia was realized. We have verified the operability of the experimental units and achieve up to 80% efficiency SCR. The final section describes the progress of the experiment and its results. It is recommended a few minor adjustments to improve stabile operation of unit INTEQ II.

L'objectif principal de cette thèse a été d'expérimenter de nouvelles voies d'exfoliation des feuillets de graphène dans des matrices polysaccharides telles que la cellulose et le chitosane dopé avec des nanoparticules d'or (Au). Notre stratégie a été d'explorer de nouvelles voies de greffage de molécules et de macromolécules sur des feuillets d'oxyde de graphène (GO). Dans un premier temps, nous avons donc oxydé un graphite commercial par la méthode de Hummers qui est apriori la méthode la plus simple à mettre en oeuvre pour produire une suspension stable de feuillets d'oxyde de graphène totalement exfoliés dans l'eau. L'intérêt de cette oxydation est l'obtention de fonctions acide carboxylique et époxyde susceptibles d'être fonctionnalisées en deux étapes par l'éthylénediamine puis par un polysaccharide tel que la cellulose. En effet, afin d'améliorer la compatibilité du graphite oxydé avec des matrices organiques telle que la cellulose, l'idée est de lui greffer des chaînes polysaccharides. Ces résultats ont permis de mettre en évidence l'exfoliation partielle des feuillets de graphène après fonctionnalisation et l'obtention d'un taux de greffage massique d'environ 35% pour la cellulose. La conductivité électrique des nano-composites correspondants a aussi été étudiée par des mesures diélectriques à des températures variées. L'augmentation de la conductivité électrique après la fonctionnalisation du graphite oxydé a mis en évidence une solvo-thermoréduction simultanément à la fonctionnalisation. Enfin, le dopage de ce matériau par des particules d'or a permis d'obtenir une conductivité électrique de 1.60 10-4 S m-1. En ce qui concerne le matériau composite à base de chitosane, la démarche scientifique a été la même que pour l'analogue cellulose, le taux de greffage massique a été d'environ 68% et nous avons en plus testé son activité catalytique vis-à-vis de la conversion du 4-Nitrophénol en 4-Aminophénol et les résultats obtenus ont été très satisfaisants / The main objective of this thesis has been to experiment a new ways of exfoliation of graphene sheets in polysaccharide matrices such as cellulose and chitosan doped with gold nanoparticles (Au). Our strategy was to explore new routes for the grafting of molecules and macromolecules onto graphene oxide (GO). First, we have oxidized commercial graphite by the method of Hummers which is a priori the simplest method to implement to produce a stable suspension of graphene oxide sheets totally exfoliated in water. The advantage of this oxidation is the formation of carboxylic acid and epoxy functional groups onto the graphite surface that can be functionalized in two stages by ethylenediamine and then by a polysaccharide such as cellulose. Indeed, in order to improve the compatibility of graphite oxide with organic matrix such as cellulose, the idea is to graft it onto polysaccharide chains. These results made it possible to demonstrate the partial exfoliation of the graphene sheets after functionalization and to obtain a percentage of grafting of about 35wt% for cellulose. The electrical conductivity of the corresponding nanocomposites has also been studied by dielectric measurements at various temperatures. The increase of the electrical conductivity after the functionalization of graphite oxide showed a solvo-thermo reduction simultaneously with the functionalization. Finally, the doping of this material by gold particles made it possible to obtain an electrical conductivity of 1.60 10-4 S m-1. Concerning chitosan-based composite materials, the scientific approach was the same as cellulose substrate and we obtained a percentage of grafting of 68wt%. In addition, its catalytic activity for the conversion of 4-Nitrophenol to 4-Aminophenol was of high efficiency