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La catalyse hétérogène influe sur la cinétique des réactions chimiques pour favoriser la formation de produits souhaités. Appliquée à la dépollution atmosphérique, elle permet de réduire considérablement l'émission de polluants. Son plus grand succès public est d'ailleurs sans conteste le pot catalytique pour les moteurs à essence. Malgré ce succès, beaucoup reste à faire pour améliorer la dépollution à basse température et pour des conditions d'utilisations très différentes telles que celles imposées par les moteurs Diesel et "lean burn".<p><p>Lors de ce travail nous nous sommes intéressés à ces sujets. Tout d'abord, nous avons étudié l'effet du SO2 sur la réduction catalytique sélective des NOx sur des catalyseurs Ag/Al2O3 dans les conditions des moteurs Diesel. Le dioxyde de soufre est reconnu comme un poison de catalyseurs. Dans cette thèse, nous avons étudié un effet promoteur du SO2. Les catalyseurs qui ont fait l’objet de ce travail ont été préparés au laboratoire. Nous avons fait varier différents paramètres tels que la température, la nature de l'hydrocarbure ou encore la concentration de SO2 afin de mieux cerner cet effet promoteur. Nous avons mis en évidence que cet effet promoteur est observable lorsque le propène est utilisé comme réducteur, alors qu'avec le propane il s'agit plutôt d'un effet négatif du SO2.<p><p>Le deuxième sujet étudié dans ce travail est l'oxydation du CO sur des catalyseurs Au/TiO2, soit préparés au laboratoire, soit fournis comme référence du World Gold Council. Ces catalyseurs offrent l’avantage de pouvoir oxyder le CO à basse température, ce qui pourrait résoudre le problème de la pollution liée au démarrage à froid des automobiles. Ces catalyseurs subissent une désactivation que nous avons analysée par spectroscopie infrarouge (DRIFT et FTIR). Une étude XPS-SIMS de catalyseurs ayant des activités différentes nous a permis de mettre en évidence des concentrations de sodium différentes sur ces catalyseurs. Dans cette thèse, nous nous sommes plus particulièrement intéressés à l'influence du potassium. Pour mettre en évidence l'influence de celui-ci sur l'activité catalytique, des catalyseurs Au/TiO2 furent préparés en absence stricte d'alcalins et d'alcalino-terreux pour ajouter par après, de manière contrôlée, les quantités souhaitées de potassium. La composition des catalyseurs préparés fut contrôlée par XPS-SIMS. Il s'avère que la présence de potassium permet d'accroître l'activité catalytique, néanmoins il semble y avoir une concentration optimale de potassium qui varie en fonction de la composition/morphologie du catalyseur Au/TiO2 au départ, c'est-à-dire sans modification par ajout de potassium.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

The subject of this study is the effect of in-cylinder selective non-catalytic reduction (SNCR) of NOx emissions in diesel exhaust gas by means of direct injection of aqueous urea ((NH2)2CO) into the combustion chamber. A single cylinder diesel test engine was modified to accept an electronically controlled secondary common rail injection system to deliver the aqueous urea directly into the cylinder during engine operation. Direct in-cylinder injection was chosen in order to ensure precise delivery of the reducing agent without the risk of any premature reactions taking place. Unlike direct in-cylinder injection of neat water, aqueous urea also works as a reducing agent by breaking down into ammonia (NH3) and Cyanuric Acid ((HOCN)3). These compounds serve as the primary reducing agents in the NOx reduction mechanism explored here. The main reducing agent, aqueous urea, was admixed with glycerol (C3H8O3) in an 80-20 ratio, by weight, to function as a lubricant for the secondary injector. The aqueous urea injection timing and duration is critical to the reduction of NOx emissions due to the dependence of SNCR NOx reduction on critical factors such as temperature, pressure, reducing agent to NOx ratio, Oxygen and radical content, residence time and NH3 slip. From scoping engine tests at loads of 40 percent and 80 percent at 1500 rpm, an aqueous urea injection strategy was developed. The final injection strategy chosen was four molar ratios, 4.0, 2.0, 1.0 and 0.5 with five varying injection timings of 60, 20, 10, 0, and -30 degrees after top dead center (ATDC). In addition to the base line and aqueous urea tests, water injection and an 80-20 water-glycerol solution reduction agent tests were also conducted to compare the effects of said additives as well. The comparison of baseline and SNCR operation was expected to show that the urea acted as a reducing agent, lowering NOx emissions up to 100% (based on exhaust stream studies) in the diesel exhaust gas without the aid of a catalyst. The data collected from the engine tests showed that the aqueous urea-glycerol solution secondary had no effect on the reduction of NOx and even resulted in an increase of up to 5% in some tests. This was due to the low average in-cylinder temperature as well as a short residence time, prohibiting the reduction reaction from taking place. The neat water and water-glycerol solution secondary injection was found to have a reduction effect of up to 59% on NOx production in the emissions due to the evaporative cooling effect and increased heat capacity of the water.

The Atlanta Inspection and Maintenance program ultimately aims to reduce on-road vehicular emission, a major source of air pollution. The program enforces eligible vehicles to be inspected and repaired, if necessary, before the annual registration renewal. However, various factors can influence the program implementation with respect to the motorists, inspectors, and testing technology. This research explores some of these factors by using empirical data from the Continuous Atlanta Fleet Evaluation project, the inspection transaction records, the Atlanta Household Travel Survey, and the U.S. Census Bureau. The study discusses policy implications of findings from the three essays and offers related recommendations. The first essay examines whether the higher income of a vehicle owner decreases the odds of the vehicle failing the first inspection. Findings show that vehicles owned by low-income households are more likely to fail the first inspection of the annual test cycle. However, after controlling for the vehicle characteristics, the odds of failing the first inspection are similar across households. This suggests that the maintenance behaviors are approximately the same for high- and low-income households. The second essay explains the motorists' decisions in selecting their inspection stations using a random utility model. The study finds that motorists are likely to choose the inspection stations that are located near their houses, charge lower fees, and can serve a large number of customers. Motorists are less likely to choose the stations with a relatively high failure ratio especially in an area of low station density. Moreover, motorists do not travel an extra mile to the stations with lower failure ratio. Understanding choices of vehicle owners can shed some light on the performance of inspection stations. The third essay investigates the validity and reliability of the on-board diagnostic generation II (OBD II) test, a new testing technology required for 1966 and newer model year vehicles. The study compares the inspection results with the observed on-road emission using the remote sensing device (RSD) of the same vehicles. This research finds that the agreement between the RSD measurement and the OBD II test is lower for the relatively older or higher use vehicle fleets