Les travaux présentés dans cette thèse concernent le développement d’un procédé de stockage d’énergie thermique haute température par voie thermochimique en vue d’une application dans une centrale solaire à concentration. Un état de l’art des technologies de stockage d’énergie thermique haute température par voie thermochimique a permis de définir le couple réactionnel et la technologie les mieux adaptés au procédé. Ainsi, la réaction réversible Ca(OH)2(s) = CaO(s) + H2O(g) est mise en oeuvre dans un réacteur à lit fluidisé. Une étude expérimentale a permis de démontrer la faisabilité du procédé en stockant et en déstockant l’énergie à une même température et en mettant en oeuvre 50 cycles de charge/décharge de l’énergie sans perte de réversibilité. L’utilisation d’un modèle monodimensionnel couplant les phénomènes chimiques, thermiques et hydrodynamiques à l’intérieur du réacteur a permis de mettre en évidence l’influence des conditions opératoires sur les performances du système. Les premiers pas vers une extrapolation industrielle font l’objet de la dernière partie de ces travaux, en présentant l’analyse énergétique d’une centrale solaire à concentration intégrant le procédé de stockage développé et en présentant une étude expérimentale mettant en oeuvre un solide de type industriel dans le réacteur. / This PhD thesis concerns the development of a high temperature thermochemical heat energy storage process for an application in concentrated solar power plants. A literature review allows the identification of both the best reaction couple and technology to operate the process. Thus, the Ca(OH)2(s) = CaO(s) + H2O(g) reversible reaction is carried out in a fluidized bed reactor. The experimental study demonstrated the process feasibility. Thermal energy has been charged and discharged at the same temperature and 50 cycles have been performed without any loss of reversibility. A 1D model coupling the chemical, thermal and hydrodynamic phenomena inside the reactor has been developed to study the operating parameter effects on the process performance. The last section of this work deals with the first steps towards an industrial scale-up. An energetic analysis of a concentrated solar power plant integrating the developed storage process is detailed as well as the reactions implementation with an industrial solid.

Exposure to atmospheric conditions results of deterioration in historic monuments. and their stones. Limestone conservation presents many problems that have to be investigated in detail. In this study, limestone deterioration and development of its conservation treatments were investigated through examination of the statues carved from karstic limestones in Nemrut Dag Monument. The decay mechanisms that had major roles in their deterioration during two thousand years of exposure to atmospheric conditions and the development of their conservation treatments involved several types of analyses that were carried out in the field and in the laboratory. Exposed surfaces of limestones having karstic veins, interior crack surfaces were examined and compared with relatively undeteriorated interior parts. Similar limestones from the geological formations nearby were artificially deteriorated by salt crystallization and were also examined for comparison. Standard physical and physicomechanical tests, petrographical analysis, XRD, SEM-EDX and FTIR were used during those examinations. Swelling nature of clays in limestones and their control were quantified by CEC measurements. The micro structure of limestone was observed to be composed of micritic calcite with karstic veins of sparitic calcite crystals. Some karstic zones were found to be preferred sites of dissolution and precipitation of calcium carbonate where swelling action of clays and widening of cracks occurred. Iron oxides that moved through those zones, as well as biological activity were also found to contribute to those phenomena. Preparation of high concentrations of nanodispersive calcium hydroxide solutions was achieved for the conservation treatments of the deteriorated limestone. Success of treatments with nanodispersive Ca(OH)2 solutions targeted to the decay zones were discussed in terms of their ability to control the swelling action of clays, carbonation of nanodispersive solution, and improvement in the physicomechanical properties of treated limestone.

A mineração do carvão fóssil gera grandes volumes de rejeitos que podem ser responsáveis por graves danos ambientais, entre os quais a Drenagem Ácida de Minas (DAM) decorrente da oxidação da pirita (FeS2) na presença de água e ar. Este percolado apresenta um baixo pH, rico em íons sulfato e ferro, bem como outros metais solúveis, como alumínio, manganês e zinco. Atualmente, o tratamento mais utilizado para este efluente é a precipitação/neutralização. Contudo, este processo muitas vezes é ineficiente para a remoção de manganês. Assim, o objetivo geral deste trabalho foi realizar o tratamento da Drenagem Ácida de Minas, visando à remoção de metais, com foco especial na remoção do íon manganês, utilizando as etapas de precipitação e, após, a troca iônica com zeólitas sintetizadas a partir de cinzas leves de carvão. A metodologia deste trabalho compreendeu duas etapas: 1°) síntese da zeólita NaP1, a partir de cinzas leves de carvão de Candiota por processo hidrotérmico e sua caracterização, 2°) caracterização da DAM, seguido de tratamento por precipitação/neutralização, e por troca iônica - zeólitas. O estudo foi aplicado para uma DAM proveniente da região carbonífera de Santa Catarina. Os resultados dos testes de caracterização do produto da síntese demonstraram a formação da zéolita NaP1, com CTC de 2,3 meq g-1. A DAM apresentou resultados típicos, com pH baixo, elevadas concentrações de Fe e sulfato e valores de manganês de 45,15 mg L-1. Os resultados do tratamento inicial mostraram que o tratamento do efluente por precipitação/neutralização, em pH 6,0, com Ca(OH)2, promove a remoção total de Al, Fe e Zn, contudo a concentração de manganês ainda fica em 28,24 mg L-1. No tratamento por troca iônica, utilizou-se a zeólita NaP1 para a remoção do manganês restante no efluente. O tempo de contato foi de 30 min, a razão S/L de 10 g L-1. O emprego da zeólita promoveu a remoção total do manganês da DAM. O mecanismo de remoção de Mn2+ ocorre por troca iônica na faixa de pH neutra e por precipitação superficial em valores de pH acima de 8,5. Em condições de laboratório, o custo do tratamento com zeólitas foi o dobro do tratamento por precipitação/neutralização. O tratamento com a utilização de zeólitas, seria uma alternativa visando a diminuição do consumo de cal hidratada com elevação do pH e remoção do Mn residual. / The mining of fossil coal generates large volumes of waste that may be responsible for serious environmental damage, including the acid mine drainage (AMD) resulting from oxidation of pyrite (FeS2) in the presence of water and air. This percolated has a low pH, rich in sulphate ions and iron as well as other soluble metals such as aluminum, manganese and zinc. Nowadays the most common treatment for this wastewater, is precipitation/neutralization. However, this process is inefficient for the removal of manganese. Thus the general aim this study was the treatment of acid mine drainage, aiming the removing metals, with special focus on removal of manganese ion, using the steps of precipitation and after the ion exchange with synthesized zeolites from fly ash coal. The methodology of this work included two steps: 1°) synthesis zeolite NAP1 from fly ash coal of Candiota by hydrothermal process and their characterization, 2°) characterization of AMD treatment followed by precipitation/neutralization and ion exchange-zeolite. The study was applied for a AMD from the coalfield of Santa Catarina. The results of the characterization tests of the synthesis product showed the formation of the zeolite NaP1, CEC from 2.3 meq g-1. The AMD showed typical results with low pH, high concentration of Fe and sulfate and manganese values 45.15 mg L-1. The results of the initial treatment from precipitation/neutralization showed that treatment of effluent by precipitation/neutralization at pH 6.0 with Ca(OH)2 promotes complete removal of Al, Fe e Zn, however the concentration is still in the manganese 28.24mg L-1. In the treatment by ion exchange, the zeolite NaP1 was used for the remaining manganese removal in wastewater. The contact time was 30 min, the ratio S/L 10 g L-1. The use of zeolite promoted the complete removal of manganese from AMD. The manganese removal by ion exchange mechanism occurs in the neutral range and surface precipitation in values above 8.5. In laboratory conditions, the cost of treatment with zeolite was double treatment by precipitation/neutralization. The treatment with use of zeolite would be an alternative aiming to decrease consumption of hydrated lime with increased pH and removing the residual Mn.

A mineração do carvão fóssil gera grandes volumes de rejeitos que podem ser responsáveis por graves danos ambientais, entre os quais a Drenagem Ácida de Minas (DAM) decorrente da oxidação da pirita (FeS2) na presença de água e ar. Este percolado apresenta um baixo pH, rico em íons sulfato e ferro, bem como outros metais solúveis, como alumínio, manganês e zinco. Atualmente, o tratamento mais utilizado para este efluente é a precipitação/neutralização. Contudo, este processo muitas vezes é ineficiente para a remoção de manganês. Assim, o objetivo geral deste trabalho foi realizar o tratamento da Drenagem Ácida de Minas, visando à remoção de metais, com foco especial na remoção do íon manganês, utilizando as etapas de precipitação e, após, a troca iônica com zeólitas sintetizadas a partir de cinzas leves de carvão. A metodologia deste trabalho compreendeu duas etapas: 1°) síntese da zeólita NaP1, a partir de cinzas leves de carvão de Candiota por processo hidrotérmico e sua caracterização, 2°) caracterização da DAM, seguido de tratamento por precipitação/neutralização, e por troca iônica - zeólitas. O estudo foi aplicado para uma DAM proveniente da região carbonífera de Santa Catarina. Os resultados dos testes de caracterização do produto da síntese demonstraram a formação da zéolita NaP1, com CTC de 2,3 meq g-1. A DAM apresentou resultados típicos, com pH baixo, elevadas concentrações de Fe e sulfato e valores de manganês de 45,15 mg L-1. Os resultados do tratamento inicial mostraram que o tratamento do efluente por precipitação/neutralização, em pH 6,0, com Ca(OH)2, promove a remoção total de Al, Fe e Zn, contudo a concentração de manganês ainda fica em 28,24 mg L-1. No tratamento por troca iônica, utilizou-se a zeólita NaP1 para a remoção do manganês restante no efluente. O tempo de contato foi de 30 min, a razão S/L de 10 g L-1. O emprego da zeólita promoveu a remoção total do manganês da DAM. O mecanismo de remoção de Mn2+ ocorre por troca iônica na faixa de pH neutra e por precipitação superficial em valores de pH acima de 8,5. Em condições de laboratório, o custo do tratamento com zeólitas foi o dobro do tratamento por precipitação/neutralização. O tratamento com a utilização de zeólitas, seria uma alternativa visando a diminuição do consumo de cal hidratada com elevação do pH e remoção do Mn residual. / The mining of fossil coal generates large volumes of waste that may be responsible for serious environmental damage, including the acid mine drainage (AMD) resulting from oxidation of pyrite (FeS2) in the presence of water and air. This percolated has a low pH, rich in sulphate ions and iron as well as other soluble metals such as aluminum, manganese and zinc. Nowadays the most common treatment for this wastewater, is precipitation/neutralization. However, this process is inefficient for the removal of manganese. Thus the general aim this study was the treatment of acid mine drainage, aiming the removing metals, with special focus on removal of manganese ion, using the steps of precipitation and after the ion exchange with synthesized zeolites from fly ash coal. The methodology of this work included two steps: 1°) synthesis zeolite NAP1 from fly ash coal of Candiota by hydrothermal process and their characterization, 2°) characterization of AMD treatment followed by precipitation/neutralization and ion exchange-zeolite. The study was applied for a AMD from the coalfield of Santa Catarina. The results of the characterization tests of the synthesis product showed the formation of the zeolite NaP1, CEC from 2.3 meq g-1. The AMD showed typical results with low pH, high concentration of Fe and sulfate and manganese values 45.15 mg L-1. The results of the initial treatment from precipitation/neutralization showed that treatment of effluent by precipitation/neutralization at pH 6.0 with Ca(OH)2 promotes complete removal of Al, Fe e Zn, however the concentration is still in the manganese 28.24mg L-1. In the treatment by ion exchange, the zeolite NaP1 was used for the remaining manganese removal in wastewater. The contact time was 30 min, the ratio S/L 10 g L-1. The use of zeolite promoted the complete removal of manganese from AMD. The manganese removal by ion exchange mechanism occurs in the neutral range and surface precipitation in values above 8.5. In laboratory conditions, the cost of treatment with zeolite was double treatment by precipitation/neutralization. The treatment with use of zeolite would be an alternative aiming to decrease consumption of hydrated lime with increased pH and removing the residual Mn.

A mineração do carvão fóssil gera grandes volumes de rejeitos que podem ser responsáveis por graves danos ambientais, entre os quais a Drenagem Ácida de Minas (DAM) decorrente da oxidação da pirita (FeS2) na presença de água e ar. Este percolado apresenta um baixo pH, rico em íons sulfato e ferro, bem como outros metais solúveis, como alumínio, manganês e zinco. Atualmente, o tratamento mais utilizado para este efluente é a precipitação/neutralização. Contudo, este processo muitas vezes é ineficiente para a remoção de manganês. Assim, o objetivo geral deste trabalho foi realizar o tratamento da Drenagem Ácida de Minas, visando à remoção de metais, com foco especial na remoção do íon manganês, utilizando as etapas de precipitação e, após, a troca iônica com zeólitas sintetizadas a partir de cinzas leves de carvão. A metodologia deste trabalho compreendeu duas etapas: 1°) síntese da zeólita NaP1, a partir de cinzas leves de carvão de Candiota por processo hidrotérmico e sua caracterização, 2°) caracterização da DAM, seguido de tratamento por precipitação/neutralização, e por troca iônica - zeólitas. O estudo foi aplicado para uma DAM proveniente da região carbonífera de Santa Catarina. Os resultados dos testes de caracterização do produto da síntese demonstraram a formação da zéolita NaP1, com CTC de 2,3 meq g-1. A DAM apresentou resultados típicos, com pH baixo, elevadas concentrações de Fe e sulfato e valores de manganês de 45,15 mg L-1. Os resultados do tratamento inicial mostraram que o tratamento do efluente por precipitação/neutralização, em pH 6,0, com Ca(OH)2, promove a remoção total de Al, Fe e Zn, contudo a concentração de manganês ainda fica em 28,24 mg L-1. No tratamento por troca iônica, utilizou-se a zeólita NaP1 para a remoção do manganês restante no efluente. O tempo de contato foi de 30 min, a razão S/L de 10 g L-1. O emprego da zeólita promoveu a remoção total do manganês da DAM. O mecanismo de remoção de Mn2+ ocorre por troca iônica na faixa de pH neutra e por precipitação superficial em valores de pH acima de 8,5. Em condições de laboratório, o custo do tratamento com zeólitas foi o dobro do tratamento por precipitação/neutralização. O tratamento com a utilização de zeólitas, seria uma alternativa visando a diminuição do consumo de cal hidratada com elevação do pH e remoção do Mn residual. / The mining of fossil coal generates large volumes of waste that may be responsible for serious environmental damage, including the acid mine drainage (AMD) resulting from oxidation of pyrite (FeS2) in the presence of water and air. This percolated has a low pH, rich in sulphate ions and iron as well as other soluble metals such as aluminum, manganese and zinc. Nowadays the most common treatment for this wastewater, is precipitation/neutralization. However, this process is inefficient for the removal of manganese. Thus the general aim this study was the treatment of acid mine drainage, aiming the removing metals, with special focus on removal of manganese ion, using the steps of precipitation and after the ion exchange with synthesized zeolites from fly ash coal. The methodology of this work included two steps: 1°) synthesis zeolite NAP1 from fly ash coal of Candiota by hydrothermal process and their characterization, 2°) characterization of AMD treatment followed by precipitation/neutralization and ion exchange-zeolite. The study was applied for a AMD from the coalfield of Santa Catarina. The results of the characterization tests of the synthesis product showed the formation of the zeolite NaP1, CEC from 2.3 meq g-1. The AMD showed typical results with low pH, high concentration of Fe and sulfate and manganese values 45.15 mg L-1. The results of the initial treatment from precipitation/neutralization showed that treatment of effluent by precipitation/neutralization at pH 6.0 with Ca(OH)2 promotes complete removal of Al, Fe e Zn, however the concentration is still in the manganese 28.24mg L-1. In the treatment by ion exchange, the zeolite NaP1 was used for the remaining manganese removal in wastewater. The contact time was 30 min, the ratio S/L 10 g L-1. The use of zeolite promoted the complete removal of manganese from AMD. The manganese removal by ion exchange mechanism occurs in the neutral range and surface precipitation in values above 8.5. In laboratory conditions, the cost of treatment with zeolite was double treatment by precipitation/neutralization. The treatment with use of zeolite would be an alternative aiming to decrease consumption of hydrated lime with increased pH and removing the residual Mn.

Les procédés de stockage de chaleur haute température par voie thermochimique solide/gaz présentent un grand intérêt pour des applications à des centrales solaires thermodynamiques. Le couple réactif CaO/Ca(OH)2 est adapté à cette application pour des déstockages entre 350 et 550°C sous des pressions de vapeur entre 0,2 et 2bar. Les paramètres de transferts de chaleur et de masse de lits de Ca(OH)2+GNE ont été évalués au travers de corrélations et d'expérimentations. Des expérimentations ont permis d'atteindre des puissances en réaction de déstockage supérieures à 200kW.m-3 pour des durées compatibles avec les centrales solaires (1 à 15h). Un modèle 2D a été développé, validé et exploité afin d'étudier les influences couplées des différents paramètres sur les performances du TCS. Enfin, l'intérêt de différentes configurations d'intégration du TCS dans la centrale solaire ont été mis en évidence en termes de performances et de puissances thermiques échangées avec les sources et puits. / High-temperature heat storage processes using thermochemical solid/gas reaction exhibit great interest for applications in solar thermodynamic power plants. The reactive pair CaO/Ca(OH)2 is suitable for this recovery step application ranging from 350 to 550°C within steam pressures from 0.2 to 2 bar. Heat and mass transfer Ca(OH)2+GNE beds parameters were evaluated through correlations and experimentations. Experiments achieved recovery reaction powers above 200kW.m-3 for compatible durations with solar power plants (1 to 15 hours). A 2D model was developed, validated and exploited to study the coupled influences of different parameters on the performance of TCS. Finally, the benefit of different configurations of TCS integration within the solar power plant have been highlighted in terms of thermal performances and sources and sinks power exchanges.

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