Le réchauffement climatique principalement dû aux émissions importantes de CO₂, gaz à effet de serre de référence, encourage les chercheurs à trouver des solutions pour lutter contre ce phénomène. Les techniques consistant à capter et stocker ou valoriser le CO₂ sont des solutions pertinentes, mais qui nécessitent d'avoir du CO₂ le plus pur possible. Parmi ces techniques, l'oxycombustion parait assez prometteuse pour produire du CO₂ en forte concentration. Toutefois, selon la nature du combustible et la pureté de l'oxygène, certains polluants peuvent apparaître tels que le CO et les NOx. Pour réaliser cette purification, la catalyse est un moyen efficace permettant de transformer simultanément le NO et le CO respectivement en N₂ et CO₂. L'objectif de cette étude est donc, de mettre au point des catalyseurs actifs pour la réduction des NOx en N₂ par le CO, dans un milieu oxydant et en présence d'eau. Deux types de catalyseurs ont été choisis : les métaux nobles (Pd, Pt, Rh) supportés et les oxydes de métaux de transition (Co, Cu, Al). Les résultats obtenus montrent que les catalyseurs à base de Pt sont plus performants et que leur activité catalytique augment pour les échantillons supportés sur un support neutre (SiO₂) ou réductible (TiO₂) que ce soit en présence ou en absence d'eau. Les oxydes mixtes de métaux de transition, obtenus par voie hydrotalcite, montre que la nature du cation bivalent joue un rôle important. Les oxydes mixtes Co-Cu ont montré une meilleure activité que les matériaux composés d'un seul de ces deux éléments. Cependant, l'ajout d'eau dans le flux réactionnel conduit à une baisse d'activité des catalyseurs contenant du Cu. / Global warming, mainly due to high CO₂ emissions, reference greenhouse gas, motivates researchers to find solutions to combat this phenomenon. The techniques of capturing and storing or reuse of CO₂ are revelant solutions, but which require a CO₂ as pure as possible. Among these techniques, oxyfuel combustion seems promising enough to produce CO₂ in high concentration. However, depending on the nature of the fuel and the oxygen purity, some pollutants may appear such as CO and NOx. To carry out this purification, catalysis is an effective means for simultaneously converting NO and CO respectively into N₂ and CO₂. The objective of this study is to develop active catalysts for NOx reduction in N₂ by CO, in oxidizing conditions and presence of water. Two types of catalysts were chosen : supported noble metals (Pd, Pt, Rh) and transition metal oxides (Co, Cu, Al). The results obtained show that the Pt-based catalysts were more efficient and that their catalytic activity increases for the samples supported on a neutral support (SiO₂) or reducible (TiO₂) whether in the presence or absence of water. The mixed oxides of transition metals, obtained by hydrotalcite, show that the nature of the bivalent cation plays an important role. Co-Cu mixed oxides showed better activity than materials composed of only one of these two elements. However, the addition of water to the reaction flow led to a decrease in activity of the Cu-containing catalysts.

O uso de combustíveis fósseis para a geração de energia, especificamente carvão mineral, ainda dominará a matriz energética mundial por algumas décadas. No Brasil, entretanto, apesar de sua vasta disponibilidade, o carvão mineral segue ocupando uma tímida posição na matriz. Ao mesmo tempo, há uma considerável geração de resíduos de biomassa oriundos de atividades agrícolas, que poderiam ser incorporados ao uso do carvão na geração termoelétrica de energia. Sobre o uso de combustíveis fósseis na geração termoelétrica e a consequente emissão de CO2, a ainda insipiente tecnologia de oxicombustão aparece como possibilidade de geração de emissões quase-zero de CO2. Diante disso, esta tese tem como objetivo estudar os aspectos envolvidos na adaptação da combustão em leito fluidizado borbulhante para a oxicombustão de carvão mineral e biomassa. Para tanto, inicialmente, realiza-se uma estimativa da possibilidade do uso de resíduos de biomassa, especificamente os provenientes da cadeia produtiva de madeira e casca de arroz, em sistemas de combustão no estado do Rio Grande do Sul. Estes combustíveis são, então, utilizados na combustão com ar atmosférico em planta piloto, com capacidade de 0,25 MWt de leito fluidizado borbulhante, para posterior comparação com a oxicombustão dos mesmos combustíveis. As comparações foram realizadas quanto ao balanço de massa balanço de energia e questões fluidodinâmicas. A influência dos principais parâmetros de processo na transição de combustão com ar atmosférico para a oxicombustão foi analisada quanto à possibilidade de minimizar a entrada de ar falso no sistema. A manutenção de pressões negativas mostrou-se indesejável na oxicombustão, especialmente quando é realizada a adaptação de plantas já existentes. Os resultados indicaram uma forte influência do ajuste da válvula de recirculação dos gases, da potência do ventilador e da vazão de gases no sistema na minimização da entrada de ar falso. A partir do ajuste das condições operacionais, foi possível a obtenção de uma concentração de 59,6% vol. de CO2 nos gases de combustão. / The fossil fuels use for energy generation, especially coal, will dominate the world energy matrix for decades. However, in Brazil, coal still occupies a timid position in spite of its extensive disponibility. At the same time, there is a considerable generation of wastes from agricultural activities that could be incorporated to coal as fuels on thermoelectric energy processes, in special for a decentralized system configuration. Yet, by considering the use of fossil fuels on thermoelectric generation and the consequent CO2 emission, there is the oxyfuel combustion technology that has appeared as an option for near-zear CO2 emissions by promoting its capture. From this perspective, this work has the objective of studying the aspects that involve the retrofit of bubbling fluidized bed combustion to oxyfuel combustion by using coal and biomass wastes as fuels. In this sense, an estimative of the use of biomass wastes, especially wood wastes and rice husk, on combustion systems in the State of Rio Grande do Sul is firstly proceeded. These fuels are used on air combustion in a 0,25 MWt bubbling fluidized bed pilot plant for comparison to oxyfuel combustion with the fuels used. Such comparisons where done by applying material balance, energy balance and fluid dynamics analysis. The influence of the main process parameters on the retrofit of air combustion to oxyfuel combustion were analyzed concerning the air leakage minimization. Negative pressure maintenance in key points of the system was shown as an undesirable issue when retrofitting. The results indicated a strong influence of the recycling valve adjustment, fan power and gases flow on the air leakage. From operational conditions adjustment, 59,6 vol.% CO2 concentration could be achieved in the gases.

O uso de combustíveis fósseis para a geração de energia, especificamente carvão mineral, ainda dominará a matriz energética mundial por algumas décadas. No Brasil, entretanto, apesar de sua vasta disponibilidade, o carvão mineral segue ocupando uma tímida posição na matriz. Ao mesmo tempo, há uma considerável geração de resíduos de biomassa oriundos de atividades agrícolas, que poderiam ser incorporados ao uso do carvão na geração termoelétrica de energia. Sobre o uso de combustíveis fósseis na geração termoelétrica e a consequente emissão de CO2, a ainda insipiente tecnologia de oxicombustão aparece como possibilidade de geração de emissões quase-zero de CO2. Diante disso, esta tese tem como objetivo estudar os aspectos envolvidos na adaptação da combustão em leito fluidizado borbulhante para a oxicombustão de carvão mineral e biomassa. Para tanto, inicialmente, realiza-se uma estimativa da possibilidade do uso de resíduos de biomassa, especificamente os provenientes da cadeia produtiva de madeira e casca de arroz, em sistemas de combustão no estado do Rio Grande do Sul. Estes combustíveis são, então, utilizados na combustão com ar atmosférico em planta piloto, com capacidade de 0,25 MWt de leito fluidizado borbulhante, para posterior comparação com a oxicombustão dos mesmos combustíveis. As comparações foram realizadas quanto ao balanço de massa balanço de energia e questões fluidodinâmicas. A influência dos principais parâmetros de processo na transição de combustão com ar atmosférico para a oxicombustão foi analisada quanto à possibilidade de minimizar a entrada de ar falso no sistema. A manutenção de pressões negativas mostrou-se indesejável na oxicombustão, especialmente quando é realizada a adaptação de plantas já existentes. Os resultados indicaram uma forte influência do ajuste da válvula de recirculação dos gases, da potência do ventilador e da vazão de gases no sistema na minimização da entrada de ar falso. A partir do ajuste das condições operacionais, foi possível a obtenção de uma concentração de 59,6% vol. de CO2 nos gases de combustão. / The fossil fuels use for energy generation, especially coal, will dominate the world energy matrix for decades. However, in Brazil, coal still occupies a timid position in spite of its extensive disponibility. At the same time, there is a considerable generation of wastes from agricultural activities that could be incorporated to coal as fuels on thermoelectric energy processes, in special for a decentralized system configuration. Yet, by considering the use of fossil fuels on thermoelectric generation and the consequent CO2 emission, there is the oxyfuel combustion technology that has appeared as an option for near-zear CO2 emissions by promoting its capture. From this perspective, this work has the objective of studying the aspects that involve the retrofit of bubbling fluidized bed combustion to oxyfuel combustion by using coal and biomass wastes as fuels. In this sense, an estimative of the use of biomass wastes, especially wood wastes and rice husk, on combustion systems in the State of Rio Grande do Sul is firstly proceeded. These fuels are used on air combustion in a 0,25 MWt bubbling fluidized bed pilot plant for comparison to oxyfuel combustion with the fuels used. Such comparisons where done by applying material balance, energy balance and fluid dynamics analysis. The influence of the main process parameters on the retrofit of air combustion to oxyfuel combustion were analyzed concerning the air leakage minimization. Negative pressure maintenance in key points of the system was shown as an undesirable issue when retrofitting. The results indicated a strong influence of the recycling valve adjustment, fan power and gases flow on the air leakage. From operational conditions adjustment, 59,6 vol.% CO2 concentration could be achieved in the gases.

O uso de combustíveis fósseis para a geração de energia, especificamente carvão mineral, ainda dominará a matriz energética mundial por algumas décadas. No Brasil, entretanto, apesar de sua vasta disponibilidade, o carvão mineral segue ocupando uma tímida posição na matriz. Ao mesmo tempo, há uma considerável geração de resíduos de biomassa oriundos de atividades agrícolas, que poderiam ser incorporados ao uso do carvão na geração termoelétrica de energia. Sobre o uso de combustíveis fósseis na geração termoelétrica e a consequente emissão de CO2, a ainda insipiente tecnologia de oxicombustão aparece como possibilidade de geração de emissões quase-zero de CO2. Diante disso, esta tese tem como objetivo estudar os aspectos envolvidos na adaptação da combustão em leito fluidizado borbulhante para a oxicombustão de carvão mineral e biomassa. Para tanto, inicialmente, realiza-se uma estimativa da possibilidade do uso de resíduos de biomassa, especificamente os provenientes da cadeia produtiva de madeira e casca de arroz, em sistemas de combustão no estado do Rio Grande do Sul. Estes combustíveis são, então, utilizados na combustão com ar atmosférico em planta piloto, com capacidade de 0,25 MWt de leito fluidizado borbulhante, para posterior comparação com a oxicombustão dos mesmos combustíveis. As comparações foram realizadas quanto ao balanço de massa balanço de energia e questões fluidodinâmicas. A influência dos principais parâmetros de processo na transição de combustão com ar atmosférico para a oxicombustão foi analisada quanto à possibilidade de minimizar a entrada de ar falso no sistema. A manutenção de pressões negativas mostrou-se indesejável na oxicombustão, especialmente quando é realizada a adaptação de plantas já existentes. Os resultados indicaram uma forte influência do ajuste da válvula de recirculação dos gases, da potência do ventilador e da vazão de gases no sistema na minimização da entrada de ar falso. A partir do ajuste das condições operacionais, foi possível a obtenção de uma concentração de 59,6% vol. de CO2 nos gases de combustão. / The fossil fuels use for energy generation, especially coal, will dominate the world energy matrix for decades. However, in Brazil, coal still occupies a timid position in spite of its extensive disponibility. At the same time, there is a considerable generation of wastes from agricultural activities that could be incorporated to coal as fuels on thermoelectric energy processes, in special for a decentralized system configuration. Yet, by considering the use of fossil fuels on thermoelectric generation and the consequent CO2 emission, there is the oxyfuel combustion technology that has appeared as an option for near-zear CO2 emissions by promoting its capture. From this perspective, this work has the objective of studying the aspects that involve the retrofit of bubbling fluidized bed combustion to oxyfuel combustion by using coal and biomass wastes as fuels. In this sense, an estimative of the use of biomass wastes, especially wood wastes and rice husk, on combustion systems in the State of Rio Grande do Sul is firstly proceeded. These fuels are used on air combustion in a 0,25 MWt bubbling fluidized bed pilot plant for comparison to oxyfuel combustion with the fuels used. Such comparisons where done by applying material balance, energy balance and fluid dynamics analysis. The influence of the main process parameters on the retrofit of air combustion to oxyfuel combustion were analyzed concerning the air leakage minimization. Negative pressure maintenance in key points of the system was shown as an undesirable issue when retrofitting. The results indicated a strong influence of the recycling valve adjustment, fan power and gases flow on the air leakage. From operational conditions adjustment, 59,6 vol.% CO2 concentration could be achieved in the gases.

No description available.

Die Herleitung des Unterschieds zwischen globaler und lokaler Stöchiometriezahl für den Oxyfuel-Prozess hat gezeigt, dass gleiche lokale Stöchiometriezahlen bei variierendem Rezirkulationsanteil unterschiedliche globale Stöchiometriezahlen zur Folge haben. In dieser Arbeit wird vorgeschlagen, die Bezeichnung der Zustandspunkte im Oxyfuel-Prozess mit den Sauerstoffkonzentrationen am Brennkammereintritt bzw. -austritt zu verbinden. Für den Sauerstoffanteil am Brennkammereintritt (z.B. 30 vol.-%) und den Restsauerstoff am Brennkammerende (z.B. 4 vol.-%) folgt zum Bespiel die Bezeichnung Oxyfuel 30 mit 4 % Restsauerstoff. Diese Bezeichnung ist eindeutig und kann das Lambda – als Beschreibung der Stöchiometrie im konventionellen Betrieb – ablösen. Für eine Vielzahl an Punkten sind Verbrennungsversuche mit Trockenbraunkohle und Sauerstoff durchgeführt worden. Ein stabiler Betrieb der Versuchsanlage der TU Dresden wurde zwischen Oxyfuel 17 und Oxyfuel 33 erreicht. Die Untersuchungen haben nachgewiesen, dass die Rezirkulation des feuchten Abgases für die Verbrennung unkritisch ist. Die Schwefeldioxid-Emissionen sind abhängig von den variierenden Reaktionstemperaturen im Kennfeld, dem Restsauerstoff am Brennkammerende und der Rezirkulation des Abgases. Mit der Belagssondenmessung von Aschepartikeln im Abgasstrom wurde gezeigt, dass auch andere Komponenten (z.B. Chlor) im Oxyfuel-Prozess aufkonzentriert werden. Diese erhöhten Konzentrationen werden zu neuen Anforderungen in der Werkstoffauswahl führen. Für das Einschwingverhalten der Abgaszusammensetzung beim Umschalten von konventioneller Verbrennung zu Oxyfuel-Prozess-Fahrweise hat sich gezeigt, dass für diese Staubfeuerungs-Versuchsanlage ein einfaches Rührkesselmodell geeignet ist.

Les progrès technologiques des dispositifs expérimentaux ainsi que les récentes avancées pour la simulation des spectres Raman à haute température rendent aujourd’hui possible la mise en oeuvre d’une technique de mesures multi-espèces de température et de concentration uniquement fondée sur l’ajustement des spectres mono-coups de diffusion Raman spontanée collectés au sein des flammes turbulentes. Dans cette étude, cette stratégie de post-traitement, associée à une chaîne de mesure spécifique, est développée selon plusieurs axes pour permettre l’extension des mesures à des cas de flammes ordinairement hostiles aux mesures classiques Rayleigh/Raman résolues par inversion matricielle ou par méthode hybride. Dans une flamme diphasique d’éthanol, une thermométrie fondée sur l’ajustement des spectres de N2 a été mise en place afin de s’affranchir des contraintes liées à la diffusion de Mie des gouttes. L’intégration d’une thermométrie Raman à partir du spectre du méthane ainsi que d’une procédure de minimisation de l’émission de C2 dans le post-traitement des spectres ont permis la réalisation de cartographies multi-scalaires (température et toutes espèces majoritaires) dans toute la zone de recirculation d’une flamme turbulente légèrement fuligineuse générée par un brûleur bluff-body. Une thermométrie fondée sur la minimisation du spectre Raman de CO2 a également été développée et éprouvée au cours d’une campagne de mesures dans une installation d’échelle semi-industrielle reproduisant les conditions d’oxycombustion des cycles de turbines à gaz dans l’objectif de la capture et de la séquestration du CO2. / Recent progress in experimental devices and simulation of high-temperature Raman spectra enable the implementation of a spectral fitting method to solve single-shot Spontaneous Raman Scattering spectra collected in turbulent flames. In this study, this post-processing method, associated to a specific experimental set-up, has been developed to extend measurements to several cases of non-Raman friendly flames where matrix inversion or hybrid methods are usually limited. In a two-phase flame, N2 Raman thermometry has been used to overcome issues from Mie scattering of droplets. The implementation of a CH4 Raman thermometry and a minimization procedure of C2 emission in the data post-processing allowed the achievement of multi-scalar cartographies (temperature and all major species) throughout the recirculation zone of a slightly sooting turbulent flame stabilized on a bluff-body burner. A thermometry based on the minimization of CO2 Raman spectrum has also been developed and tested during a measurement campaign in a semi-industrial scale installation designed for the study of oxyfuel gas turbine cycle in the aim of carbon capture and sequestration.

Global energy demand is predicted to rise in the coming decades, necessitating a shift to renewable energy sources to mitigate greenhouse gas emissions. However, due to the inability to supply renewable energy around the clock, it is estimated that only by adding an important technology, carbon capture and storage (CCS), it could be possible to reduce 80% of the 1990s greenhouse gas emissions. CCS aims to reduce anthropogenic carbon emissions by capturing CO2 from flue gases, transporting, and permanently storing or reutilizing industrially. The CCS approach includes three technologies: post-combustion capture, pre-combustion capture, and oxyfuel combustion, with the latter being the emphasis of this thesis. Based on the case study of Mälarenergi’s Refused-derived waste-fired CHP plant, this thesis investigates the viability of converting existing non-fossil fueled CHP plants to oxyfuel combustion. A thorough technical investigation based on analyzing the impact of oxyfuel combustion on system performance was conducted through system modeling using a process simulator, Aspen plus. The model in this thesis considers the development of an air separation unit (ASU), a CHP plant, and a cryogenic CO2 purification unit (CPU). All of which are validated through calibration and comparison with real-world data and similar work. To investigate the influence of employing oxyfuel combustion on the generation of both heat and electricity, two different scenarios were comprised, including recirculating flue gas before and after flue gas condensation. In addition, an analysis of the oxygen purity was conducted to assess the most optimal parameters with the least impact on system performance. Moreover, a detailed eco- nomic assessment comprising the costs of integrating oxyfuel combustion was also conducted. The findings of this thesis show that integrating waste incineration CHP plants with oxyfuel combustion for CO2 capture entails promising features under the condition of 97% oxygen purity and a flue gas recirculation system taking place after flue gas condensation. This is owing to (i) modest imposed energy penalty of approximately 8.7%, (ii) high CO2 recovery ratio, around 92.4%, (iii) total investment cost of approximately 554 M$ during a 20-year lifetime, and (iv) cost of captured CO2 of around 76 $/ton. Aside from system modeling, this thesis pre- sents an overview of the current state-of-the-art technology on the different separation and capture mechanisms. It is important to highlight that the goal of this thesis is not to provide a comprehensive review but rather to present an overall picture of the maturity of the different mechanisms. The findings point to the cryogenic separation mechanism as the most mature technology for both oxygen production and capturing of CO2 during oxyfuel combustion.

The topic of this thesis is carbon dioxide (CO2) capture and storage (CCS), which is a technology that is currently being promoted by industries, scientists and governments, among others, in order to mitigate climate change despite a continued use of fossil fuels. Because of the complex nature of CCS and the risks it entails, it is controversial. The aim of this thesis is to analyse how the technology may be further developed in a responsible manner. In the first part of the thesis different methods for capturing CO2 from industrial processes as well as power plants are analysed. The aim is to identify early opportunities for CO2 capture, which is considered important because of the urgency of the climate change problem. Three potential early opportunities are studied: i) capturing CO2 from calcining processes such as cement industries by using the oxyfuel process, ii) capturing CO2 from pressurised flue gas, and iii) capturing CO2 from hybrid combined cycles. Each opportunity has properties that may make them competitive in comparison to the more common alternatives if CCS is realised. However, there are also drawbacks. For example, while capturing CO2 from pressurised flue gas enables the use of more compact capture plant designs as well as less expensive and less toxic absorbents, the concept is neither suitable for retrofitting nor has it been promoted by the large and influential corporations. The second part of the thesis has a broader scope than the first and is multidisciplinary in its nature with inspiration from the research field of Science and Technology Studies (STS). The approach is to critically analyse stakeholder percep-tions regarding CCS, with a specific focus on the CCS experts. The thesis sheds new light on the complexity and scientific uncertainty of CCS as well as on the optimism among many of its proponents. Because of the uncertain development when it comes to climate change, fossil fuel use and greenhouse gas emissions, the conclusion is that CCS has to be further developed and demonstrated. A responsible strategy for a future development of CCS would benefit from: i) a search for win-win strategies, ii) increasing use of appropriate analytical tools such as life-cycle analysis, iii) a consideration of fossil fuel scarcity and increasing price volatility, iv) funding of unbiased research and v) increasing simultaneous investments in long-term solutions such as renewable energy alternatives and efficiency improvements. / QC 20100727