Dans le contexte de l’écologie industrielle, l’objectif du projet est de récupérer du dioxyde de carbone à partir des fumées d’incinérateur de déchets industriels dangereux pour le valoriser en tant que matière première. La technologie de captage du CO2, la plus adaptée pour des fumées de postcombustion, est l’absorption du CO2 par des alcanolamines. Les fumées d’incinération de déchets dangereux présentent des particularités qui peuvent nuire au bon fonctionnement des unités de captage. Ainsi, la composition des fumées d’une usine d’incinération est caractérisée par une forte concentration en dioxygène, et enfin à la présence de NOx et SOx liée aux déchets industriels spéciaux qu’elle incinère. Le premier objectif est de déterminer l’influence des polluants (NOx, SOx) sur la dégradation de l’amine (MEA) et le second objectif est d’étudier l’impact des polluants sur la vitesse (ou flux) d’absorption du CO2 dans un solvant. / In the context of industrial symbiosis, the goal of this project is to reuse the carbon dioxide from the incinerator gas as a commercial substance. The most suitable technology of CO2 capture from postcombustion gas is the chemical absorption by alkanolamines. Some characteristics of waste incinerator gas may affect the performances of CO2 capture process. The composition of gas from industrial waste incinerator plant is characterized by a high concentration of oxygen and the presence of NOx and SOx. The first goal is to determine the influence of pollutants like NOx and SOx on the degradation of the amine and the second objective is to study the impact of pollutants on the CO2 absorption kinetics in a solvent.

Les réglementations sur les NOx émis par les avions sont sévères. Les techniques les réduisant ont des inconvénients. Pour les supprimer, deux pistes sont explorées. La première modifie l'architecture des chambres de combustion et les stabilise par une cavité. La seconde dope le kérosène au ralenti.Peu d'information est disponible sur les mécanismes de stabilisation et sur la structure de flamme des Trapped Vortex Combustor. Pour y remédier, un TVC est construit. L'étude de l'écoulement à froid ainsi que l'étude temporellement résolue de la flamme, mettent en avant les éléments stabilisateurs et déstabilisateurs. L'impact de la structure de flamme sur les émissions est évalué.La seconde partie porte sur l'effet de l'ajout d'hydrogène et de gaz de reformeur dans une chambre conventionnelle. Malgré une légère augmentation des émissions de NOx, l'ajout de composés hydrogénés réduit fortement les émissions de CO, augmente la stabilité et réduit la limite d'extinction pauvre. / Environmental standards on aircraff NOx emissions are strict. Technics for reducing them have drawbacks. Two options are explored in this study to supress them. The first one is to fundamentally change the current combustion chamber architecture, to stabilize them by a cavity, the second, to dope fuel at idle.Little information on the mechanisms of stabilization and on the flame structure on Trapped Vortex Combustor is available. To remedy this, a TVC is built. The stabilizing ans destabilizing parameters are pointed out by the cold flow investigation and the temporally resolved study of the combustion. The impact of the flame structure on pollutant emissions is also considered.The second part of this stud, deals with the addition of pure hydrogen an of reformer gas in a conventional combustuion chamber. Despite a slight increase in NOx emissions, the addition of hydrogenated compounds reduces drastically CO emissions, increases the flame stability and reduces the LBO limit.

Cette thèse est consacrée à l’amélioration des capacités de prédiction des émissions d’oxydes d’azote (NO et NO2) des foyers de combustion aéronautiques. Les travaux, exclusivement numériques, consistent d’abord dans une étude de la cinétique chimique responsable des émissions polluantes. Cetteétude conduit à l’écriture d’un modèle, nommé NOMANI (pour Nitrogen Oxide emission model with one-dimensional MANIfold), basé sur l’approche PCM-FPI (pour Presumed Conditional Moments - Flame Prolongation of ILDM) avec une variable de progrès additionnelle afin calculer l’avancement de la chimie azotée une fois la chimie carbonée à l’équilibre. Différentes validations sur des configurations laminaires simples puis des flammes de laboratoire de Sandia sont présentées. Les résultats en terme de structure de flamme et d'émission de monoxyde d’azote sont confrontés aux mesures expérimentales. Le dernier volet de ces travaux, disponible uniquement dans la version confidentielle du manuscrit, consiste dans le développement d’un modèle de prédiction de polluants associé au modèle TF-LES (pour Thickening Flame for Large Eddy Simulation). Le modèle développé est ensuite appliqué à des calculs d’une chambre de combustion aéronautique. / This thesis is focused on the prediction capabilities of nitrogen oxides (NO and NO2) for numerical tools applied to aeronautical combustion chambers. The modeling work is based on a study of the chemical kinetic that produced the pollutant emissions. This study leads to a model, called NOMANI (Nitrogen Oxide emission model with one-dimensional MANIfold), based on PCM-FPI (Presumed Conditional Moments - Flame Prolongation of ILDM) with an additional progress variable to compute the NO evolution once the carbon chemistry is at the equilibrium. Several benchmarks and test-cases (laminar and turbulent flames) are gathered in this study : Sandia flame have been computed and satisfactory comparisons with measurements are obtained. The last part of this work, only available in the confidential version of the manuscript, is the development of a model to predict pollutant associated with the model TF-LES (for Thickening Flame for Large Eddy Simulation). This model is then applied to computations of a aeronautical combustion chambers.

En ville, les parcs de stationnement couverts représentent un milieu confiné dans lequel s'accumule une pollution importante et complexe. Ils constituent également une source de pollution pour leurs abords puisqu'aucune obligation de traitement n'est imposée sur la qualité de l'air rejeté dans l'atmosphère par les systèmes de ventilation. Dans le cadre du traitement de l'air, l'utilisation d'un biofiltre végétalisé, faisant intervenir des bactéries et des plantes en association, constitue une solution innovante contribuant à l'amélioration de la qualité de l'air en ville en réduisant la dispersion de polluants gazeux dans l'atmosphère. Dans un contexte de « recherche et développement », l'objectif est de comprendre le fonctionnement biologique et physico-chimique du biofiltre dans le but d'en améliorer la maitrise opérationnelle. Le caractère innovant de l'étude porte sur le traitement d'importants volumes d'air viciés contenant de faibles concentrations de polluants, tels que les NOx et les COV (de l'ordre de 100 à 200 µg/m3), par un biofiltre planté d'épaisseur modeste. L'utilisation d'une unité pilote de biofiltration a permis d'évaluer l'influence de la présence de plante, ainsi que la nécessité d'un apport d'engrais, sur les capacités d'épuration d'un tel système. Afin d'optimiser les volumes d'air traités tout en limitant l'empreinte au sol des biofiltres végétalisés, la vitesse de passage de l'air a été augmentée et l'épaisseur de garnissage réduite. Le rôle des bactéries indigènes a été caractérisé par une étude fonctionnelle des communautés bactériennes impliquées dans la dégradation des NOx et des TEX d'une part, et par une étude quantitative et qualitative de la communauté bactérienne totale, en utilisant des approches de biologie moléculaire, telles que l'amplification par PCR en temps réel et le pyroséquençage à partir de l'ADN métagénomique / In town, underground car parks are confined spaces in witch large and complex pollution are accumulated. They are also a source of contamination of the external environment since the treatment of the air pumped out by ventilation system sis not regulated. In the framework of air treatment, using planted biofilter, combining bacteria and plants, is an innovative solution contributing to the improvement of urban air quality by reducing the dispersion of gaseous pollutants in the atmosphere. In a « research and development » context, the objective is to understand the biological and physico-chemical operation for improving operational control. This innovative study focuses on the treatment of high volumes of air containing a low concentrations of pollutants, such as NOx, VOCs (about 100 à 200 µg.m-3) through a thin planted biofilter. The use of a pilot-scale unit of biofiltration allowed to evaluate the influence of the plant, as well as the necessity of a fertilization, on the removal efficiency of such a system. In order to maximize the volumes of treated air while limiting the footprint of the planted biofilters, the superficial gas velocity has been increased and the thickness of the packing material decreased. The indigenous bacteria have been characterized by a functional study of the bacterial communities involved in the degradation of NOx and TEX on one part, and by a quantitative and qualitative study of the total bacterial community on the other part, by using molecular biology approaches, such a real-time PCR amplification, and pyrosequencing from metagenomic DNA. Results on pilot-scale unit have shown a removal efficiency greater than 97%, in all environmental conditions tested. Consequently, it seems possible to treat high volumes of air containing low concentrations of TEX through a thin planted biofilter. The presence of plants does not seem to have short-term impacts on the removal efficiency when a fertilizer promotes the nitrogen availability in the packing material. The evaluation of the global microbiological functioning showed the potential of microbial communities in the biodegradation of NOx and TEX in planted biofilters. The indigenous bacterial communities of the packing material and the mound of soil are rapidly able to adapt to the functioning conditions of such a system

Nearly half of the electrical power produced in the United States is generated with coal. Coal power is inexpensive and reliable, but coal combustion releases harmful pollutants including NOx and SOx into the atmosphere if not controlled. CO2, a greenhouse gas, is also released during coal combustion and may contribute to global warming. A promising technology enabling carbon capture is oxy-coal combustion. During oxy-combustion, coal is burned in an atmosphere of O2 and recycled flue gas to eliminate nitrogen which makes up the majority of air-combustion flue gas. Oxy-combustion flue gas is mainly composed of CO2 and H2O. H2O can be condensed out of the gas, and the CO2 can then be captured and permanently stored relatively easily. The composition of the gas inside an oxy-fired boiler will be different due to the absence of nitrogen and the recycling of flue gas. Corrosive sulfur and chlorine gas species concentrations will be higher, and CO and NOx concentrations will be effected. An understanding of the differences in gas concentrations is critical to oxy-combustion boiler design. Four different pulverized coals were combusted in a reactor under staged and unstaged oxy-combustion conditions with warm recycled flue gas (420°F) to simulate conditions in an oxy-fired coal boiler. The gas composition was measured in the reducing and oxidizing zones for staged combustion, and in the same locations, 57 cm and 216 cm from the burner, for unstaged combustion. The results were compared to the results from similar staged air-combustion experiments using the same coals and burner. CO concentrations were higher for staged oxy-combustion compared to air-combustion, and the increase was more substantial for lower rank coals. H2S concentrations in the reducing regions were also higher, and the fraction of gas phase sulfur measured as H2S was higher for oxy-combustion. SO2 concentrations were 2.9 to 3.8 times as high as air-combustion concentrations. The measured conversion of coal sulfur to SO3 was lower for oxy-combustion, and ranged from 0.61% to 0.98%. The average fraction of coal sulfur measured in the gas phase was 84%, 80%, and 85% for staged oxy-combustion, unstaged oxy-combustion, and staged air-combustion respectively. HCl concentrations were 2.8 to 3.1 times higher in the staged oxy-combustion oxidizing zone, and a smaller fraction of coal chlorine was measured in the reducing zone. On average 70.8%, 79.5%, and 71.1% of the coal chlorine was measured as HCl for staged oxy-combustion, unstaged oxy-combustion, and staged air-combustion respectively. The fractions of coal chlorine and sulfur measured in the gas phase for staged combustion were not significantly affected by combustion media. Some staged oxy-combustion NO concentrations were lower than air-combustion concentrations while others were slightly higher, and NO emission rates were much lower due to recycling NO through the burner.

NOx-sensorn är grundläggande i det moderna efterbehandlingssystemet och dess pålitlighet är avgörande för att kunna leva upp till rådande emissionslagkrav. Livslängden samt sensorns beteende i slutet av denna varierar betydligt. Om en NOx sensor med oberäkneligt beteende inte upptäcks av fordonets styrsystemet kan det orsaka omfattande verkstadsbesök eller i värsta fall brott mot emissionslagkrav. Examensarbetet involverar identifiering av olika sensorfellägen, tidiga tecken till dessa fellägen, förstå och identifiera förhållanden mellan olika sensorparametrar och analysera sensorbeteendet vid sensorlivslängdens slutskede. NOx sensorn är en relativt ny sensor och fordonsindustrin har ännu inte en fullständig förståelse för dess beteende. Litteraturstudien täcker olika fellägena så som fastnat värde, förskjutet värde, förstärkning av värdet, felaktiga svängningar samt långsam respons. Även effekterna av åldrande i NOx sensorn beskrivs. Litteraturstudien diskuterar också diagnoser av sensorer i allmänhet samt diagnoser specifikt för NOx sensorer. Uppsatsarbetet involverar också en experimentell studie där NOx sensorer utsätts för statiska och fluktuerande gasflöden i en motortestbädd. Fellägen i NOx sensorer kan observeras i parametrarna för NOx-värde och oxidationsnivå. I den version av NOx sensorn som användes observerades det också att parametrarna felaktig NOx och felaktig O2 visar samma felkod samtidigt. Dock är inte parametrarna för felaktig NOx och felaktig O2 relaterade till parametrarna för värmningsstatus, felaktig värmare och värmeelementets temperatur. Sensorns status gällande ogiltiga NOx-mätningar är större än eller lika med antalet ogiltiga O2-mätningar. Resultatet gäller framför allt sensormodell Continental 2.8 NOx sensorer. Även logik för en monitor gällande felaktiga svängningar utvecklas baserat på standardavvikelse och NOx statusparametern för ogiltig mätning. / The NOx sensor is essential in the modern after-treatment system and the reliability of the sensor is crucial for any emission-based legislation. The life span of a sensor varies a lot as well as the behaviour previous to its end of life. If a NOx sensor with erratic behaviour is not discovered by the control system it may cause extensive workshop effort or in worst case exceed legal requirements. The thesis work involves identifying different sensor failure modes, precursors to these failure modes, understanding and identifying relationships between different sensor parameters, and analysing the sensor behaviour especially towards the end of life. The NOx sensor is a relatively new sensor and the vehicle industry does not yet have a complete understanding of its behaviour. The literature study covers the different failure modes namely stuck, offset, gain, oscillations, and slow response and their causes along with the effects of ageing in NOx sensors. It also discusses the diagnosis of faulty sensors in general and faulty NOx sensors. The thesis work also involves an experimental study where the NOx sensors are subjected to static and transient gas flow tests in an engine testbed. Failure modes in NOx sensors are observable in NOx concentration and actual oxidation measurement parameters. It was also observed in the version of the NOx sensor used that Error NOx and Error O2 parameters show the same fault code at the same time. Although, the Error NOx and Error O2 parameters are not related to the heater parameters, Heater status, Error heater, and Temperature of heating element. The number of invalid flags set in NOx status is greater than or equal to the number of invalid flags in O2 status. The mentioned parameters are concerning Continental 2.8 NOx sensors. The logic for the oscillatory fault monitor is developed based on standard deviation and an invalid flag check on the NOx status parameter.

Master of Science / Department of Mechanical and Nuclear Engineering / Kirby S. Chapman / The increased emissions monitoring requirements of industrial gas turbines have created a demand for less expensive emissions monitoring systems. Typically, emissions monitoring is performed with a Continuous Emissions Monitoring System (CEMS), which monitors emissions by direct sampling of the exhaust gas. An alternative to a CEMS is a system which predicts emissions using easily measured operating parameters. This system is referred to as a Parametric Emissions Monitoring System (PEMS). A review of the literature indicates there is no globally applicable PEMS. Because of this, a PEMS that is applicable to a variety of gas turbine manufacturers and models is desired. The research presented herein includes a literature review of NOx reduction techniques, NOx production mechanisms, current PEMS research, and combustor modeling. Based on this preliminary research, a combustor model based on first-engineering principles was developed to describe the NOx formation process and relate NOx emissions to combustion turbine operating parameters. A review of available literature indicates that lean-premixed combustion is the most widely-used NOx reduction design strategy, so the model is based on this type of combustion system. A review of the NOx formation processes revealed four well-recognized NOx formation mechanisms: the Zeldovich, prompt, nitrous oxide, and fuel-bound nitrogen mechanisms. In lean-premixed combustion, the Zeldovich and nitrous oxide mechanisms dominate the NOx formation. This research focuses on combustion modeling including the Zeldovich mechanism for NOx formation. The combustor model is based on the Siemens SGT-200 combustion turbine and consists of a series of well-stirred reactors. Results show that the calculated NOx is on the same order of magnitude, but less than the NOx measured in field tests. These results are expected because the NOx calculation was based only on the Zeldovich mechanism, and the literature shows that significant NOx is formed through the nitrous oxide mechanism. The model also shows appropriate trends of NOx with respect to various operating parameters including equivalence ratio, ambient temperature, humidity, and atmospheric pressure. Model refinements are suggested with the ultimate goal being integration of the model into a PEMS.

Aortic dissection is a detrimental disease with a high mortality. However, the mechanisms regulating the susceptibility to aortic dissection remain unknown. We hypothesize that endothelial oxidative stress due to the activation of the reactive oxygen species (ROS)-generating Nox2 enzyme may play an important role in the development of aortic dissection. To investigate this, we generated transgenic mice (C57BL/6J background) with endothelial specific over-expression of Nox2 (Nox2 Tg) under the control of a tie-2 promoter. Expression of the human Nox2 transgene was confirmed by qRT-PCR to be found only in endothelial cells (EC) isolated from transgenic mice, and not in Wt EC or vascular smooth muscle cells (VSMC) and macrophages isolated from either genotype. Wild-type (Wt) littermates and Nox2 Tg male mice (22-24 weeks old, n=11) were treated with saline or Ang II (1mg/kg/day) via subcutaneous mini-pump for 28 days. There was no significant difference in the pressor responses to Ang II between Wt and Nox2 Tg mice (Wt 121±7mmHg vs. Nox2-Tg 122±6mmHg). However, 5/11 Nox2 Tg mice developed aortic dissections compared to 0/11 Wt mice (P<0.05). Immunohistochemistry revealed significant increases in endothelial VCAM-1 expression, MMP activity and CD45+ inflammatory cell recruitment in the aortas of Nox2 Tg mice after 5 days of Ang II infusion. Inflammatory cell recruitment was confirmed by FACS analysis of cells from digested aortas (P<0.05). Explanted aortas from Nox2-Tg mice had significantly greater secreted pro-inflammatory cytokine, Cyclophilin A (CypA) both at baseline and after 5 days of Ang II infusion compared to Wt littermates. Compared to primary Wt EC and VSMC, Nox2-Tg primary EC, but not primary VSMC, had increased ROS production which was accompanied by increased endothelial CypA secretion and ERK1/2 activation. Furthermore, conditioned media from Nox2-Tg EC induced greater ERK1/2 phosphorylation compared to conditioned media from Wt controls. Knockdown of CypA from sEND.1 endothelial conditioned media by siRNA knockdown abolished VSMC Erk1/2 phosphorylation. In conclusion, we demonstrate for the first time that a specific increase in endothelial ROS through the over-expression of Nox2 was sufficient to induce aortic dissection in response to Ang II stimulation. Endothelial secreted CypA could be the signalling mechanism by which increased endothelial ROS regulates the inflammatory response and the susceptibility to aortic dissection.

In recent years, the causal relationship between inflammation and cancer has gained wider acknowledgement and acceptance. While various types of immune cells are involved in the process of inflammation, macrophages represent the major inflammatory component of many tumors. Derived from circulating monocytes, these cells migrate to tumor sites in response to molecular cues present within the tumor microenvironment. Once there, interactions with neoplastic cells shape the differentiation and functional orientation of macrophages into two phenotypically distinct subsets: the “classically” activated M1 macrophages and the “alternatively” activated M2 macrophages. The preeminent paradigm in macrophage-related cancer research is that within the tumor stoma, macrophages acquire an M2 phenotype characterized by production of pro-angiogenic factors, ECM degrading enzymes and up-regulation of anti-inflammatory responses, thereby promoting tumor progression. M1 macrophages, on the other hand are thought to exert anti-tumorigenic effects due to their production of pro-inflammatory cytokines, and reactive oxygen species (ROS). While the generation of ROS during immune responses is an important aspect of immune regulation and host defense, excessive ROS production has been implicated in the pathogenesis of various degenerative diseases, including cancer. Yet, despite the well-established role of M1 macrophages in generating high levels of ROS via NADPH oxidase (NOX), M1 macrophages are still largely viewed as anti-tumorigenic. Hence, this study reevaluates the complex interaction between prostate cancer (PCa) cells and tumor-associated macrophages (TAMs), and operates on the premise that PCa cells promote a pro-tumor microenvironment, denoted by increased inflammation and oxidative stress, in part, through M1 macrophage-mediated, NOX-derived ROS production. Accordingly, immunofluorescent analysis of prostate tissue microarrays demonstrated an influx of M1 macrophages in prostate carcinoma. Immature monocytes co-cultured with the poorly tumorigenic prostate cell line, LNCaP, demonstrated changes in morphology and protein expression consistent with M1 macrophage polarization. PCa cells co-cultured with M1 macrophages displayed significantly higher intracellular ROS levels. Furthermore, M1-mediated ROS generation through NOXs increased prostate cell invasiveness and anchorage-independent growth. Taken together, results from this study suggest a potentially novel pro-tumorigenic function of M1 macrophages in early PCa progression, and aid in understanding the complex role of inflammation in cancer.

Nitrogen oxides (NOx) are atmospheric pollutants that pose a serious threat to both the environment and human health. Although catalytic deNOx technologies for engines working under stoichiometric air-to-fuel ratios (i.e., most gasoline engines) are already available, their performance is unsatisfactory under excess air conditions like those under which diesel engines operate. The selective catalytic reduction of NOx with hydrocarbon reductants (HC-SCR) is a potential deNOxsolution for diesel engines, whose operating temperatures are 150-500 ºC. Given that is unlikely for a single catalyst to show acceptable activity throughout this entire temperature span, the use of two catalysts is proposed in this dissertation. Whereas several catalysts active at high temperatures (>300 ºC) are already available, a catalyst showing an acceptable performance at low temperatures (<300 ºC) is yet to be found. Platinum group metals (PGMs) supported on activated carbon have been identified as promising low temperature HC-SCR catalysts. However, these materials show three main drawbacks: 1) the propensity of the carbon support to undergo combustion in an oxidizing environment, 2) a narrow temperature window of operation; and 3) a high selectivity towards N2O (as opposed to N2). To address the first limitation, the use of multi-walled carbon nanotubes (MWCNTs) as the support has been investigated and found to yield catalysts displaying a higher resistance to oxidation. Further, the acid activation of MWCNTs prior to their use as catalyst support has been explored, following reports than link carrier acidity with improved catalyst performance. In turn, the use of PGM alloys as the active phase has been examined as a means to improve catalyst activity and selectivity. Additionally, kinetic, spectroscopic and mechanistic studies have been performed in an attempt to probe structure-activity relationships in the MWCNTs-based formulations showing the best deNOx performance. The fundamental insights gained through these studies may inform further improvements to HC-SCR catalysts. Finally, the synthesis of the most promising formulations has been scaled-up using commercial metal monoliths as the catalyst substrate and the resulting monolithic catalysts have been tested in a diesel engine for activity in the HC-SCR reaction.