Le dioxyde de carbone, provenant de la combustion d’énergies fossiles, est l’un plus important gaz à effet de serre. La réduction des émissions de CO2 à l’atmosphère s’imposant, une solution consiste en la capture et la séquestration du CO2 par oxy-combustion. Avant l’étape de séquestration, le CO2 doit être purifié. Les procédés de séparation des gaz nécessitent une bonne connaissance des propriétés thermodynamiques des équilibres entre phases. C’est pourquoi un nouvel appareil expérimental, permettant l’étude de la solubilité d’un mélange de gaz (CO2, O2, NOx, SO2) dans des solutions aqueuses, a été développé. Dans un premier temps, l’étude du système CO2-eau a permis de valider l’appareil expérimental pour les domaines de température et de pression de l’étude (293 ,15-393,15 K, jusqu’à 5 MPa). Ensuite, les données sur le système CO2-eau-NaOH étant rares dans la littérature, ce système a été étudié. Les données expérimentales obtenues ont été comparées à un modèle développé dans l’étude. Les modèles de coefficient d’activité de Pitzer et de NRTL électrolyte sont comparés. La dernière étape de l’étude est l’optimisation des paramètres du modèle NRTL-e par ajustement sur les données expérimentales. / Production of carbon dioxide from burning fossil fuel participates in the global warming. This issue generates a growing interest for CO2 capture and storage from oxy fuel combustion. Before the sequestration step, the CO2 has to be purified from impurities. Separation processes require a good knowledge of thermodynamics properties of phase equilibria. In this context a new experimental device was designed and set up in the LaTEP to allow the study of the solubility of gas mixture involved in CO2 capture and storage processes (CO2, O2, NOx, SO2). The apparatus was, first, validated by studying the CO2-water system in the temperature range from 293.15 K to 393.15 K and at pressure up to 5 MPa. Then, the CO2-water-NaOH was studied because few data are available in the scientific literature. Experimental data obtained was compared with a model developed in this work. This model is based on a thermodynamic description of physical chemical phenomena occuring in a vapour liquid system. Two model of activity coefficient are compared (Pitzer and electrolyte-NRTL). The last step of this study is the parameter optimization for e-NRTL.

In this study the catalytic pyrolysis and combustion characteristics of Turkish coal samples in O2/N2 and O2/CO2 (oxy-fuel conditions) ambient conditions were explored and the evolution of emissions during these tests was investigated using non-isothermal Thermo-gravimetric Analysis (TGA) technique combined with Fourier Transform Infrared (FTIR) spectroscopy. Potassium carbonate (K2CO3), calcium hydroxide (Ca(OH)2), iron (III) oxide (Fe2O3) and iron (III) chloride (FeCl3) were employed as precursors of catalysts to investigate the effects of potassium (K), calcium (Ca) and iron (Fe). Furthermore the effects of these catalysts on calorimetric tests of Turkish coal samples were investigated. TGA-FTIR pyrolysis tests were carried out in 100 % N2 and 100 % CO2 ambient conditions which are the main diluting gases in air and oxy-fuel conditions. Lignite pyrolysis tests revealed that the major difference between pyrolysis in these two ambient conditions was observed beyond 720

A new method of power production, called pressurized oxy-fuel combustion, burns coal with CO2 and oxygen, rather than air, bringing us closer to the end goal of developing zero emission coal-fired utility boilers. However, high-pressure, high-temperature systems such as these are under-studied, and their behavior is difficult to measure. An accurate model for previously untested conditions requires data for validation. The heat release profile of flames and their radiative intensity is one of the key data sets required for model validation of an oxy-coal combustion system. A radiometer can be used to obtain the necessary radiative heat flux data. However, several studies show significant measurement errors of past radiometer designs. This work focuses on developing a narrow angle radiometer that can be used to describe radiative heat transfer from a pressurized oxy-coal flame. The sensitivity of the instrument to outside environmental influences is thoroughly examined, making it possible to obtain the axial radiative heat flux profile of the flame in a 100kW pressurized facility by accurately converting the measured quantities into radiative heat flux. Design aspects of the radiometer are chosen to improve the accuracy of radiative heat flux measurements as well as conform to the physical constraints of the 100kW pressurized facility. The radiometer is built with a 0.079-inch aperture, an 8.63-inch probe internally coated with high emissivity coating, four baffles spaced evenly down the length of the probe, no optic lens, a thermopile as the sensor, argon purge gas, and a water-cooled jacket. The radiometer has a viewing angle of 1.33 degrees. The instrument is calibrated with a black body radiator, and these calibration data are used in combination with radiation models to convert the radiometer signal in mV to radiative heat flux in kW/m2. Environmental factors affecting accuracy are studied. The results of the calibration data show that the radiometer measurements will produce a calculated heat flux that is accurate to within 5.98E-04 kW/m2.

Oxy-fuel combustion technology, which is based on burning coal in a mixture of oxygen and recycled flue gas (RFG), is suggested as one of new promising technologies for capturing CO2 from power plants. In this thesis study, the pyrolysis and combustion behaviour of various fuels including imported coal, petroleum coke, two different types of indigenous lignites, olive residue and their blends with different proportions in air and oxy-fuel conditions were investigated by using non-isothermal thermogravimetric method (TGA) coupled with Fourier-transform infrared (FTIR) spectrometer. Pyrolysis tests were carried out in nitrogen and carbon dioxide environments, which are the main diluting gases of air and oxy-fuel environment, respectively. Pyrolysis results reveal that weight loss profiles are similar up to high temperature zone in both pyrolysis environments, indicating that CO2 behaves as an inert gas in this temperature range. However, further weight loss takes place in CO2 atmosphere v after 700oC due to CO2-char gasification reaction which is observed in pyrolysis of all fuel samples. Combustion experiments were carried out in four different atmospheres / air, oxygen-enriched air environment (30 % O2 &ndash / 70 % N2), oxy-fuel environment (21 % O2 &ndash / 79 % CO2) and oxygen-enriched oxy-fuel environment (30 % O2 &ndash / 70 % CO2). Combustion experiments show that replacing nitrogen in the gas mixture by the same concentration of CO2 does not affect the combustion process significantly but leads to slight delay (lower weight loss rate and higher burnout temperature) in combustion. Overall comparison of weight loss profiles shows that higher oxygen content in the combustion environment is the dominant factor affecting the combustion rather than the diluting gas. As O2 concentration increases profiles shift through lower temperature zone, peak and burnout temperatures decrease, weight loss rate increases and complete combustion is achieved at lower temperatures and shorter times. Pyrolysis and combustion behaviour of three different fuel blends were also investigated. Results reveal synergistic interactions in combustion tests of all blends in all combustion environments. During pyrolysis and combustion tests gaseous products CO2, CO, H2O, CH4, SO2 and COS were identified in flue gas and analyzed by using FTIR. Results indicate that higher CO and COS formation take place during pyrolysis tests due to gasification reaction in CO2 atmosphere at high temperature zone. Gaseous species evolution trends in combustion tests are found specific for each fuel. However, evolution trends slightly shift to lower temperatures in oxygen-enriched conditions.

Carbon capture and storage technologies are necessary to start lowering greenhouse gas emissions while continuing to utilize existing thermal power generation infrastructure. Calcium looping is a promising technology based on cyclic calcination/carbonation reactions which utilizes limestone as a sorbent. Steam is present in combustion flue gas and in the calciner used for sorbent regeneration. The effect of steam during calcination on sorbent performance has not been extensively studied in the literature. Here, experiments were conducted using a thermogravimetric analyzer (TGA) and subsequently a dual-fluidized bed pilot plant to determine the effect of steam injection during calcination on sorbent reactivity during carbonation. In a TGA, various levels of steam (0-40% vol.) were injected during sorbent regeneration throughout 15 calcination/carbonation cycles. All concentrations of steam were found to increase sorbent reactivity during carbonation. A level of 15% steam during calcination had the largest impact. Steam changes the morphology of the sorbent during calcination, likely by shifting the pore volume to larger pores, resulting in a structure which has an increased carrying capacity. This effect was then examined at the pilot scale to determine if the phase contacting patterns and solids heat-up rates in a fluidized bed were factors. Three levels of steam (0%, 15%, 65%) were injected during sorbent regeneration throughout 5 hours of steady state operation. Again, all levels of steam were found to increase sorbent reactivity and reduce the required sorbent make-up rate with the best performance seen at 65% steam.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Um novo laboratório experimental desenvolvido para investigar a combustão de carvão em atmosferas de oxicombustão é descrito em detalhes na tese. Um reator ciclônico é utilizado para a combustão de carvões de baixo rank em condições de escoamento turbulento e com swirl, e operando em temperaturas similares às encontradas em câmaras de combustão industriais. Um sensor potenciométrico de oxigênio, instalado dentro do reator ciclônico, é utilizado para medir o consumo de oxigênio durante a combustão das amostras de carvão. Amostras de carvão com alto teor de cinzas, das minas do Leão e Bonito localizadas no sul do Brasil, e amostras de carvão linhito pré-seco (LTBK), da região da Lusácia, na Alemanha, foram submetidos à combustão em atmosferas de ar e de oxicombustão (O2/CO2/H2O). Os experimentos foram realizados em três temperaturas médias do gás de combustão: 1073, 1173 e 1273 K. Para as amostras do carvão LTBK, a oxicombustão foi composta com duas atmosferas de O2/CO2 sem vapor d’água (21/79 e 30/70) e três atmosferas de O2/CO2/H2O (30/60/10, 30/50/20 e 30/40/30) em base molar, enquanto para as amostras dos carvões Leão e Bonito, a oxicombustão foi composta com duas atmosferas de O2/CO2 (21/79 e 30/70). As amostras de carvão foram peneiradas para uma faixa de tamanho de partículas de 1250 a 2000 μm e 125 a 500 μm, e com massas de 1g e 3g. Em adição aos testes, amostras de char dos carvões Leão e LTBK foram preparadas para investigar o comportamento da combustão de suas matrizes carbonosas com diferentes níveis de matéria volátil. Primeiramente, a investigação da combustão do carvão é feita diretamente a partir das curvas de concentração de oxigênio medidas para a combustão das amostras de carvão LTBK submetidos às atmosferas de ar e oxicombustão com vapor d’água, conforme explicado no Capítulo 2 desta tese. Entretanto, devido ao grande número de experimentos realizados e a necessidade de entender a influência dos fatores, como temperatura e as composições das atmosferas oxidantes, e as interações entre esses fatores na combustão do carvão, a análise pela metodologia do Projeto de Experimentos (DoE) é aplicada nos experimentos, conforme detalhado no Capítulo 3. A reatividade dos carvões de baixo rank é investigada por meio do cálculo dos parâmetros cinéticos globais e dos coeficientes da taxa de reação de combustão do char, considerando a hipótese de um reator bem misturado, a ser verificada ao longo da investigação, conforme descrito no Capítulo 4. A partir da análise das curvas de concentração de oxigênio (Capítulos 2 e 3), os resultados mostram que a atmosfera de oxicombustão com 79% de CO2 (21/79, O2/CO2) aumenta o consumo de oxigênio para os carvões de alto teor de cinzas, Bonito e Leão, e para o carvão linhito com alto teor de voláteis (LTBK), devido à influência da reação de gaseificação do CO2 a partir de temperaturas acima de 1073 K. A partir da análise dos parâmetros cinéticos globais calculados para avaliar a reatividade dos carvões, os resultados mostram que a hipótese do reator bem misturado não é o suficiente para capturar a cinética da combustão do carvão por batelada no interior do reator ciclônico. A reatividade dos carvões investigados, através das constantes efetivas da taxa de reação, variando-se a composição da atmosfera oxidante, temperatura do gás de combustão, tamanho de partículas, massa da amostra e posição do sensor de oxigênio, têm influência do escoamento com swirl e seus termos advectivos e difusivos. / A novel laboratory facility designed to investigate coal oxy-fuel combustion is described in the present work. A cyclone chamber allows for the combustion of low-rank coal under turbulent conditions and swirling flows, covering a temperature range similar to those found on practical furnaces. A potentiometric oxygen sensor with oxide-ion conducting solid electrolytes, as stabilized zirconia, installed within the cyclone reactor, is used to measure the oxygen consumption during the combustion of coal samples. High ash coals samples, from Leão and Bonito mining sites located in South Brazil, and pre-dried lignite coal samples (LTBK), from the Lusatian region, in Germany, were burned under air and oxy-fuel (O2/CO2/H2O) atmospheres. Experiments were carried out at three average gas combustion temperatures: 1073, 1173 and 1273 K. For LTBK coal, oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70) and three O2/CO2/H2O atmospheres (30/60/10, 30/50/20 and 30/40/30) in molar basis, whereas for Leão and Bonito coals, the oxy-fuel combustion was composed with two O2/CO2 atmospheres (21/79 and 30/70). Coal samples were sieved to a size range of 1250 to 2000 μm and 125 to 500 μm and with 1g and 3g. In addition, char samples from Leão and lignite coals were prepared in order to investigate the combustion behavior of its carbon matrix for different levels of volatile matter. The investigation of coal combustion behavior is made firstly directly on the oxygen concentration curves measured for LTBK coal samples burned under air and oxy-fuel atmospheres with water vapor, as detailed in Chapter 2 of this thesis. However, due to the great number of experiments performed and the need to understand the influence of the factors, as temperature and atmosphere compositions, and the interactions between them on the coal combustion, the Design of Experiments (DoE) analysis is applied in the laboratory test facility, as developed in Chapter 3. The reactivity of low rank coals is assessed by means of global kinetic parameters and of char combustion reaction coefficients, under assumption of a well stirred reactor to be tested along the investigation, as described in Chapter 4. From the analysis of oxygen concentration curves (Chapter 2 and 3), results show that oxidizer oxy-fuel atmosphere with 79% CO2 (21/79, O2/CO2) increases the oxygen consumption for high ash coals, Bonito and Leão, and for pre-dried lignite coal, LTBK, due to the influence of CO2 gasification reaction on their coal combustion reactions from gas combustion temperatures higher than 1073 K. From the analysis of global kinetic parameters calculated to assess the coal reactivity, the results show that the hypothesis of a well stirred reactor is not enough to capture the kinetic involved in coal combustion burned in batch mode within the cyclone reactor. The coal reactivity investigated with the effective reaction rate constants for different oxidizer atmospheres, gas combustion temperatures, particle diameters, sample masses and oxygen sensor position, is influenced by the swirling flow with its advective and diffusive terms.

Carbon capture and storage technologies are necessary to start lowering greenhouse gas emissions while continuing to utilize existing thermal power generation infrastructure. Calcium looping is a promising technology based on cyclic calcination/carbonation reactions which utilizes limestone as a sorbent. Steam is present in combustion flue gas and in the calciner used for sorbent regeneration. The effect of steam during calcination on sorbent performance has not been extensively studied in the literature. Here, experiments were conducted using a thermogravimetric analyzer (TGA) and subsequently a dual-fluidized bed pilot plant to determine the effect of steam injection during calcination on sorbent reactivity during carbonation. In a TGA, various levels of steam (0-40% vol.) were injected during sorbent regeneration throughout 15 calcination/carbonation cycles. All concentrations of steam were found to increase sorbent reactivity during carbonation. A level of 15% steam during calcination had the largest impact. Steam changes the morphology of the sorbent during calcination, likely by shifting the pore volume to larger pores, resulting in a structure which has an increased carrying capacity. This effect was then examined at the pilot scale to determine if the phase contacting patterns and solids heat-up rates in a fluidized bed were factors. Three levels of steam (0%, 15%, 65%) were injected during sorbent regeneration throughout 5 hours of steady state operation. Again, all levels of steam were found to increase sorbent reactivity and reduce the required sorbent make-up rate with the best performance seen at 65% steam.

To mitigate the global greenhouse gases (GHGs) emissions, carbon dioxide (CO2) capture and storage (CCS) has the potential to play a significant role for reaching mitigation target. Oxy-fuel combustion is a promising technology for CO2 capture in power plants. Advantages compared to CCS with the conventional combustion technology are: high combustion efficiency, flue gas volume reduction, low fuel consumption, near zero CO2 emission, and less nitrogen oxides (NOx) formation can be reached simultaneously by using the oxy-fuel combustion technology. However, knowledge gaps relating to large scale coal based and natural gas based power plants with CO2 capture still exist, such as combustors and boilers operating at higher temperatures and design of CO2 turbines and compressors. To apply the oxy-fuel combustion technology on power plants, much work is focused on the fundamental and feasibility study regarding combustion characterization, process and system analysis, and economic evaluation etc. Further studies from system perspective point of view are highlighted, such as the impact of operating conditions on system performance and on advanced cycle integrated with oxy-fuel combustion for CO2 capture. In this thesis, the characterization for flue gas recycle (FGR) was theoretically derived based on mass balance of combustion reactions, and system modeling was conducted by using a process simulator, Aspen Plus. Important parameters such as FGR rate and ratio, flue gas composition, and electrical efficiency etc. were analyzed and discussed based on different operational conditions. An advanced evaporative gas turbine (EvGT) cycle with oxy-fuel combustion for CO2 capture was also studied. Based on economic indicators such as specific investment cost (SIC), cost of electricity (COE), and cost of CO2avoidance (COA), economic performance was evaluated and compared among various system configurations. The system configurations include an EvGT cycle power plant without CO2 capture, an EvGT cycle power plant with chemical absorption for CO2 capture, and a combined cycle power plant. The study shows that FGR ratio is of importance, which has impact not only on heat transfer but also on mass transfer in the oxy-coal combustion process. Significant reduction in the amount of flue gas can be achieved due to the flue gas recycling, particularly for the system with more prior upstream recycle options. Although the recycle options have almost no effect on FGR ratio, flue gas flow rate, and system electrical efficiency, FGR options have significant effects on flue gas compositions, especially the concentrations of CO2 and H2O, and heat exchanger duties. In addition, oxygen purity and water/gas ratio, respectively, have an optimum value for an EvGT cycle power plant with oxy-fuel combustion. Oxygen purity of 97 mol% and water/gas ratio of 0.133 can be considered as the optimum values for the studied system. For optional operating conditions of flue gas recycling, the exhaust gas recycled after condensing (dry recycle) results in about 5 percentage points higher electrical efficiency and about 45 % more cooling water consumption comparing with the exhaust gas recycled before condensing (wet recycle). The direct costs of EvGT cycle with oxy-fuel combustion are a little higher than the direct costs of EvGT cycle with chemical absorption. However, as plant size is larger than 60 MW, even though the EvGT cycle with oxy-fuel combustion has a higher COE than the EvGT cycle with chemical absorption, the EvGT cycle with oxy-fuel combustion has a lower COA. Further, compared with others studies of natural gas combined cycle (NGCC), the EvGT system has a lower COE and COA than the NGCC system no matter which CO2 capture technology is integrated. / QC 20111123