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Biomass fast pyrolysis liquid (bio-oil) is a cellulose based alternative fuel with the potential to displace fossil fuels in stationary heat and power applications. To better understand the combustion behavior and emissions of bio-oil, a 10 kW spray burner was designed and constructed. The effect of swirl, atomization quality, ignition source (pilot) energy, air/fuel preheat and equivalence ratio on the stability and emissions of bio-oil spray flames was investigated. A blend of 80% pyrolysis liquid and 20% ethanol by volume was used during the tests and the results were compared to burner operation with diesel. It is important to have good atomization, thorough mixing and high swirl in order to stabilize ignition, promote the burnout of bio-oil and decrease CO, hydrocarbon and particulate matter emissions. The total amount of primary air and atomizing air that can be used to improve turbulence, mixing, droplet burnout and overall combustion quality is limited by the distillable fraction and narrow lean blow-out limit associated with pyrolysis liquid. Air and fuel preheat are important for reducing hydrocarbon and CO emissions, although subsequent fuel boiling should be avoided in order to maintain flame stability. The NOx produced in bio-oil flames is dominated by the conversion of fuel bound nitrogen. The particulate matter collected during bio-oil combustion is composed of both carbonaceous cenosphere residues and ash. Under good burning conditions, the majority consists of ash. Pilot flame energy and air/fuel preheat have a weak effect on the total particulate matter in the exhaust. Generally, these results suggest that available burner parameters can be adjusted in order to achieve low hydrocarbon, CO and carbonaceous particulate matter emissions when using pyrolysis liquid. Total particulates can be further mitigated by reducing the inherent ash content in bio-oil. Comparative burner tests with diesel reveal much lower emissions for this fuel at most of the operating points considered. This is due to the fully distillable nature, better atomization and improved spray ignition characteristics associated with diesel. Because of its superior volatility, diesel can also operate over a much wider range of primary air and atomizing air flow rates compared to bio-oil.

Biomass fast pyrolysis liquid (bio-oil) is a cellulose based alternative fuel with the potential to displace fossil fuels in stationary heat and power applications. To better understand the combustion behavior and emissions of bio-oil, a 10 kW spray burner was designed and constructed. The effect of swirl, atomization quality, ignition source (pilot) energy, air/fuel preheat and equivalence ratio on the stability and emissions of bio-oil spray flames was investigated. A blend of 80% pyrolysis liquid and 20% ethanol by volume was used during the tests and the results were compared to burner operation with diesel. It is important to have good atomization, thorough mixing and high swirl in order to stabilize ignition, promote the burnout of bio-oil and decrease CO, hydrocarbon and particulate matter emissions. The total amount of primary air and atomizing air that can be used to improve turbulence, mixing, droplet burnout and overall combustion quality is limited by the distillable fraction and narrow lean blow-out limit associated with pyrolysis liquid. Air and fuel preheat are important for reducing hydrocarbon and CO emissions, although subsequent fuel boiling should be avoided in order to maintain flame stability. The NOx produced in bio-oil flames is dominated by the conversion of fuel bound nitrogen. The particulate matter collected during bio-oil combustion is composed of both carbonaceous cenosphere residues and ash. Under good burning conditions, the majority consists of ash. Pilot flame energy and air/fuel preheat have a weak effect on the total particulate matter in the exhaust. Generally, these results suggest that available burner parameters can be adjusted in order to achieve low hydrocarbon, CO and carbonaceous particulate matter emissions when using pyrolysis liquid. Total particulates can be further mitigated by reducing the inherent ash content in bio-oil. Comparative burner tests with diesel reveal much lower emissions for this fuel at most of the operating points considered. This is due to the fully distillable nature, better atomization and improved spray ignition characteristics associated with diesel. Because of its superior volatility, diesel can also operate over a much wider range of primary air and atomizing air flow rates compared to bio-oil.

High fossil fuel consumption in transportation and industry results in an increase of the emission of green-house gases. To preserve clean air, new strategies are required. The main intention is to decrease the amount of CO2 emission by using lean-burn engines while increasing the combustion efficiency and decreasing the fuel consumption. However, the lean-burn engines have high air-to-fuel ratio which complicates the reduction of the oxides of nitrogen, NOx . The emission of these highly noxious pollutants, NOx , breeds both environmental and health problems. Thus, new catalytic strategies have been steadily developed. One of these strategies is the NOx storage and reduction (NSR) catalysts. Since the reduction of the NOx under excess oxygen condition is very difficult, the NSR catalysts store the NOx until the end of the lean phase that is subsequently alternated with the rich-fuel phase during which the trapped NOx is released and reduced. To develop NSR technology, different storage materials, the coverage of these metals/metal-oxides, support materials, precious metals, temperature, etc. have been widely investigated. In this thesis, the (100) surface of BaO with dopants (K, Na, Ca and La), (100) and (110) surfaces of Li2O, Na2O and K2O are investigated as storage materials. In addition, alkali metal (Li, Na and K) loaded (001) surface of TiO2 (titania) anatase is investigated as a support material for the NOx storage and reduction catalysts. The main aim is to increase the sulfur resistance. The introduction of the dopants on the BaO (100) surface has increased the stability of the NO2 . The combination of local lattice strain and different oxidation state, which is obtained by the La doped BaO (100) surface, benefit both NO2 adsorption performance and sulfur tolerance. The binding energies of NO2 adsorption configurations over the alkali metal oxide (100) and (110) surfaces were higher than the binding energies of SO2 adsorption configurations. The stability of all of NO2 adsorption geometries on the alkali metal-loaded TiO2 (001) surface were higher than the stability of SO2 adsorption geometries. Increasing basicity enhanced the adsorption of NO2 molecule.

Pollution from automobile exhaust is one of the most major environmental problems because of increasing usage of engine technologies. Diesel and lean burn gasoline engines operate under oxygen rich (lean) conditions and they emit harmfull gases to the atmosphere (CO,CO2, NO, NO2). The control of NOx emission from exhaust has become a challenging issue in engine industry because of the worldwide environmental regulations. Therefore lean-burn NOx emission control technologies have been developed to reduce emission of harmfull gases from exhausts, and the NOx storage/reduction (NSR) catalysts is one of the most promising candidates to reduce the pollution caused by lean-burn engines. In NSR systems, NO from the emission is first oxidized to NO2 over noble metal sites (Pt, Rh, Pd) during lean-burn engine operation. After that NO2 is stored as nitrites and nitrates in alkali earth oxides (BaO,MgO, CaO) particles or monolayer which is well dispersed on a substrate (Gamma-Al2O3, TiO2, SiO2). Finally, stored NOx compound are broken into N2 and O2 on noble metal sites. The Pt/BaO/Gamma-Al2O3 system is one of the most popular subjects in literature both experimentally and theoretically since this system is known to be catalytically more active and ecient in interactions between NOx and Pt-BaO components are still not clearly explained. For this reason, in this thesis, the interaction between catalytic redox components, Pt and Rh, and the support material Gamma-Al2O3 and the eects of Pt and Rh in atomic and diatomic clusters forms on the adsorption of the NO2 molecule on the Gamma-Al2O3(100) surface have been investigated by using density functional theory (DFT).

A major opportunity for using satellite observations of tropospheric chemical concentrations is to improve our scientific understanding of atmospheric processes by integrated analysis of satellite, aircraft, and ground-based observations with global and regional scale models. One endpoint of such efforts is to reduce modeling biases and uncertainties. The idea of coupling these observations with a regional scale air quality model was the starting point of this research. The overall objective of this research was to improve the NOₓ emission inventories by integrating observations from different platforms and regional air quality modeling. Specific objectives were: 1) Comparison of satellite NO₂ retrievals with simulated NO₂ by the regional air quality model. Comparison of simulated tropospheric gas concentrations simulated by the regional air quality model, with aircraft and ground-based observations; 3) Assessment of the uncertainties in comparing satellite NO₂ retrievals with NOₓ emissions estimates and model simulations; 4) Identification of biases in emission inventories by data assimilation of satellite NO₂ retrievals, and ground-based NO, NO₂ and O₃ observations with an iterative inverse method using the regional air quality model coupled with sensitivity calculations; 5) Improvement of our understanding of NOₓ emissions, and the interaction between regional and global air pollution by an integrated analysis of satellite NO₂ retrievals with the regional air quality model. Along with these objectives, a lightning NOₓ emission inventory was prepared for two months of summer 2004 to account for a significant upper level NOₓ source. Spatially-resolved weekly NO₂ variations from satellite retrievals were compared with estimated NOₓ emissions for different region types. Data assimilation of satellite NO₂ retrievals, and ground-based NO, NO₂ and O₃ observations were performed to evaluate the NOₓ emission inventory. This research contributes to a better understanding of the use of satellite NO₂ retrievals in air quality modeling, and improvements in the NOₓ emission inventories by correcting some of the inconsistencies that were found in the inventories. Therefore, it may provide groups that develop emissions estimates guidance on areas for improvement. In addition, this research indicates the weaknesses and the strengths of the satellite NO₂ retrievals and offers suggestions to improve the quality of the retrievals for further use in the tropospheric air pollution research.

It is the need of the hour to reduce the pollutants which poison our atmosphere and harm our health. The diesel engines are the most efficient IC engines in the world today, but paradoxically, they are also the engines which create the largest amounts of NOx, the pollutant that is most difficult to control with the existing technologies. In fact, the existing technologies are unable to meet the increasingly stringent standards for NOx. Even in bio-diesels, which in the future may be adopted as an important alternative fuel, NOx is the major pollutant. Thus not having a safe and stable method for NOx removal from the diesel exhaust stream is a cause for concern. In this thesis, there has been an attempt to address this issue by means of non-thermal plasma and catalysts. In this thesis, first the performance of the three sources was evaluated individually, along with two different HV electrodes, a helical wire and a straight wire. Secondly, the efficiencies of these three different types of sources were compared. Thirdly, a catalyst (Red Mud) and an adsorbent (NaZSM5) were cascaded with the plasma reactor to enhance the performance of the NOx removal process with the AC source as it gave the best results. All the experiments were performed with real diesel engine exhaust. The conclusions drawn from the experiments are as follows: The helical electrode consumes much lower power than the straight electrode. Therefore it is energy efficient. It also causes corona inception at lower voltages due to the strong non-uniformity of its electric field. The drawbacks of the helical electrode are an excess production of NO2 .it also does not work with the HFAC source, because at high frequency, the voltage doesn’t build up owing to the presence of only a dielectric medium of 2 mm thickness between the two electrodes. The performances of the 3 sources were compared. The HVAC unit gave the best NOx removal, followed by the MPC and finally, the HFAC source. The differences in efficiencies were related to both the magnitude of the peak voltage achieved by each device and the time period. It was also seen that when the voltage was high, a better efficiency can be achieved with lower power consumption. The comparison of the sources leads us to conclude that the high voltage AC source can be used as an economic alternative for NOx control. This is because a standard AC unit is easily available at higher voltages, and contains less electrical or mechanical complexity, whereas a pulsed source is comparatively expensive and complex. The NaZSM5 zeolite showed excellent removal at room temperature as an adsorbent when cascaded after the AC source, by reducing the NO2 levels consistently. The Red Mud showed reasonable catalytic activity at 400 C with the AC source. It was also efficient in compensating for the increase in the NO2 and CO concentration in the plasma atmosphere. Hence, both Red Mud and ZSM 5 are good candidates for a hybrid plasma-adsorbent or plasma-catalyst system. The combination better NOx/CO removal is the AC energization coupled with spiral electrode with either ZSM-5 or red mud. Scaling up the plasma/ plasma- catalyst system for handling higher flow rates will be the main task next. A method to optimize the source and load matching for better power transfer to the plasma reactor from the different sources also need to be developed. The design of the compact high frequency AC source must be upgraded for higher powers.

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.

Le catalyseur quatre voies est destiné à diminuer simultanément les émissions d'hydrocarbures, de monoxyde de carbone, d'oxydes d'azote et de suies par l'intermédiaire d'un seul monolithe catalytique. Plusieurs études sur ce type de catalyseur ont montré que la présence d'oxydes d'azote entraîne une diminution de la température d'oxydation des suies. Cependant, l'effet de la présence d'eau sur l'adsorption des oxydes d'azote n'est pas encore clair, surtout en présence de suies. Les travaux présentés dans ce manuscrit ont pour but de mettre en évidence l'influence de la présence d'eau et/ou de suies sur le fonctionnement de catalyseur "piège à NOx". Les résultats obtenus montrent que la présence d'eau entraîne une inhibition de la fonction oxydante du catalyseur, une diminution de la quantité de stockage des oxydes d'azote, et une inhibition de la formation des espèces adsorbées de surface. Ces phénomènes ont été attribués à la voix réactionnelle spécifique en présence d'eau associée à l'adsorption des oxydes d'azote. Les résultats obtenus sur le mélange noir de carbone et catalyseur montrent que la présence de noir de carbone induit une diminution de stockage des oxydes d'azote. De plus, cet effet se trouve plus important en contact fort. Les expériences réalisées sur l'adsorption des oxydes d'azote en présence simultanée de noir de carbone et d'eau ont montré un effet non cumulé de l'eau et du noir de carbone. Ce phénomène a été attribué à une compétition entre l'action de l'eau qui favorise la formation de nitrate de cœur à partir des nitrates faiblement liés et l'action du noir de carbone qui tend à déstabiliser les nitrates faiblement liés pour former les carbonates.

La SCR (Selective Catalytic Reduction) permet de réduire les oxydes d'azote (NOx) à l'intérieur d'une ligne d'échappement d'un véhicule Diesel à l'aide d'une solution réductrice à base d'urée injectée en amont d'un catalyseur. L'urée est convertie en NH3 par pyrolyse et hydrolyse, et NH3 réduit les NOx enN2 sur le catalyseur. Cependant, comme cette technique met en jeu un ensemble de réactions très complexes, beaucoup de réactions parasites peuvent entraîner la formation de produits secondaires contenant de l'azote et perturber le bon déroulement du procédé. Par conséquent, l'élaboration d'une étude sur la mesure de ces produits secondaires et de leurs conditions de formation est donc essentielle pour la bonne calibration de la SCR. Si pour certains composés, les techniques de mesures sont encore à développer, dans tous les cas, on se trouve confronté à des problèmes liés au prélèvement des espèces. L'objectif de la thèse est d'identifier, de comprendre et de quantifier les phénomènes qui entrent en jeu et qui perturbent l'analyse des composés azotés dans la ligne d'échappement et dans la ligne de prélèvement. Le travail a été mené selon différents axes de recherche : la comparaison des méthodes de mesure de composés azotés en situation réelles dans les gaz d'échappement d'un moteur Diesel muni d'un catalyseur SCR, l'étude du prélèvement des composés azotés et notamment NH3 dans une ligne de prélèvement standard et la modélisation des pertes dans une ligne de prélèvement. A la fin de ce travail, nous avons évalué l'impact des conditions de prélèvements : température des gaz, composition et/ou longueur des lignes de prélèvement, sur les résultats de la mesure. Ce travail nous permet d'apporter des suggestions pour améliorer le prélèvement et les mesures des composés azotés présents à l'échappement d'un véhicule Diesel équipé d'une SCR.