[pt] Os hidratos são compostos cristalinos semelhantes ao gelo, formados por uma combinação de água e gás. A medida que a indústria de petróleo e gás natural vem se expandindo cada vez mais para águas mais profundas e geladas, a formação de hidratos em emulsões do tipo água em óleo (A/O) é um problema a ser considerado. O problema associado a formação de hidratos reside principalmente em seu elevado potencial para interromper ou prejudicar o escoamento nos dutos, o que eleva a custos proibitivos as operações de perfuração e produção. No que diz respeito a este cenário, a indústria de óleo e gás vem investindo em métodos para gerenciar o risco de formação de hidratos, de modo a prevenir um bloqueio total do escoamento. Uma das alternativas dessa estratégia é estudar a relação entre a variação de propriedades reológicas e a formação do hidrato usando um fluido modelo. Todavia, usualmente os hidratos são formados sob baixa temperatura e alta pressão, condição esta que representa um obstáculo a este tipo de estudo. A solução para tal problema é utilizar compostos que formem hidrato a pressão atmosférica, como por exemplo, o ciclopentano, que é liquido a temperatura ambiente. O presente trabalho visou analisar diferentes métodos de preparo para formação de emulsões do tipo A/O. Foram produzidas emulsões com corte de água variando de 20 a 40 por cento, com dois tipos de óleos minerais: Morlina S2 BL 10 e Morlina S2 B 150. Para todas as emulsões, foi utilizada uma mistura de surfactantes, Span 80 e AOT, com duas diferentes concentrações: 1 e 5 por cento em peso dos tensoativos. Após a produção desses fluidos modelos, estudou-se a reologia dos mesmos, sem e com ciclopentano, sendo estes últimos submetidos a condições de formação de hidratos em testes oscilatórios. / [en] Hydrates are crystalline compounds similar to the ice formed by a combination of water and gas. Once the oil and gas industry expands into deeper and icy waters, the formation of hydrates in water-in oil (w/o) emulsions should be considered. The problem associated with hydrate formation lies mainly in its high potential to stop or damage the flow in pipelines, which increases to prohibitive costs the operations of drilling and production. Regarding this scenario, the oil and gas industry has been investing in methods to manage the risk of hydrate formation, in order to prevent a total blockage of the flow. One of the alternatives of this strategy is to study the relationship between the change of rheological properties and the formation of hydrate in a fluid model. However, usually natural gas hydrates are formed under low temperature and high pressure condition, which is a barrier to this type of study. The solution to this problem is to use certain compounds that form hydrate at atmospheric pressure, such as cyclopentane, which is liquid at room temperature. This study aimed to analyze different methods of preparation for the formation of w/o emulsions. The emulsions were prepared with water cut ranging from 20 to 40 percent and with two different mineral oils: Morlina S2 BL 10 and Morlina S2 B 150. In all cases, a surfactant blend, composed by Span 80 and AOT, was added, with two different concentrations: 1 and 5 wt percent surfactant mixture in respect to the total emulsion weight. After the production of these fluid models, it was studied the rheology of those without and with cyclopentane, which were submitted to hydrate formation conditions in oscillatory tests.

No description available.

[pt] Esta tese de doutorado se propõe a estudar a reologia de pastas de hidratos composta por água e tetrahidrofurano (C4H8O - THF) em diversas conjunturas. Os hidratos de gás natural são sólidos cristalinos, análogos ao gelo, formados pela agregação de água e de gás numa determinada estrutura organizada. Sua preocupação para a Indústria de petróleo e gás deve-se ao risco potencial relacionada a área de garantia de escoamento. Assim sendo, amplos investimentos são feitos com o propósito de prevenir e avaliar os ricos da formação de hidratos. Neste contexto, a reologia é um elemento chave, pois permite detectar a formação dos hidratos a partir de variações das propriedades reológicas, sendo as mais comuns: viscosidade, módulos viscoso e elástico. Entretanto, duas condições fundamentais para o sucesso desta abordagem são relativamente difíceis de se conseguir em laboratório, a combinação de alta pressão e baixa temperatura. Inicialmente serão estudadas pastas de hidratos formadas à pressão atmosférica, ainda a temperaturas acima de 0 graus Celsius. Em outro momento, serão estudados os efeitos da adição de álcool nas pastas de hidratos e, finalmente, serão analisadas as pastas formadas em pressões acima da pressão atmosférica. Foram realizados ensaios reológicos para diferentes composições de fluidos. Alcançam-se resultados transientes e de estado estacionário, mostrando que a reologia é fortemente afetada pela aglomeração e desagregação de cristais de hidratos que ocorrem simultaneamente à medida que os hidratos se formam e as condições de contorno que cercam os experimentos. / [en] This doctoral thesis proposes to study the rheology of water hydrate and tetrahydrofuran slurries (C4H8O - THF) at different conditions. Natural gas hydrates are crystalline solids, analogous to ice, formed by the aggregation of water and gas in a given organized structure. Their concern for the oil and gas industry is due to the potential risk related to the area of flow assurance. Thus, extensive investments are made for the purpose of preventing and evaluating the risk of hydrate formation. In this context, rheology is a significant element, since it allows to detect the formation of hydrates from variations in rheological properties, the most common being: viscosity, viscous and elastic modules. However, two fundamental conditions for the success of this approach are relatively difficult to achieve in the laboratory, the combination of high pressure and low temperature. Initially will be studied hydrate pastes formed at atmospheric pressure, still at temperatures above 0 Celsius degrees. In another moment, the effects of the addition of alcohol in the hydrate pastes will be studied and, finally, the pastes formed at pressures encountered above atmospheric pressure will be analyzed. Rheological tests were performed for different fluid compositions. Transient and steady-state results are reached, showing that rheology is strongly affected by the agglomeration and disaggregation of hydrate crystals occurring simultaneously as hydrates form and the boundary conditions surrounding the experiments.

No / Hydration of five Roman and American natural cements was analyzed using X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy of cement pastes. Two cements were prepared in the laboratory by burning marls from geological sources in Poland (Folwark) and Austria (Lilienfeld). The selection of raw materials and burning conditions were optimized so that the hydraulic nature and appearance of the final burnt materials matched as closely as possible historic Roman cements widely used in the 19th and the beginning of the 20th centuries in Europe to decorate buildings. Three other cements are produced commercially: quick setting Prompt cement from Vicat, France, and Rosendale cements from Edison Coatings Inc., USA. The hydration of the cements studied was shown to comprise two distinct stages. The immediate setting and early strength is due to the formation of calcium aluminum oxide carbonate (or sulfate) hydroxide hydrates. The development of long-term strength is brought about by the formation of calcium silicate hydrates. Similarities and differences between the individual cements are discussed.

Le béton est l'un des matériaux de construction les plus utilisés au monde. Sa durabilité, ses propriétés mécaniques et chimiques en ont fait un matériau de choix dans les concepts de stockage proposés par l'Agence Nationale pour la gestion des Déchets RadioActifs (Andra), notamment pour la réalisation des ouvrages de soutènement, bouchons d'alvéoles, massifs d'appuis ou encore conditionnement des déchets. L'étude de la stabilité des phases constitutives des matériaux cimentaires est donc nécessaire au vu des quantités envisagées et de la pérennité des ouvrages, et doit considérer (i) des gammes de températures adaptées aux matrices cimentaires de confinement en contact avec des déchets exothermiques (25 à 80°C), et (ii) une échelle de temps représentative de la durée de vie d'un stockage.Le projet ThermoChimie de l'Andra vise donc à développer une base de données (BDD) thermodynamiques cohérente, permettant de modéliser l'évolution chimique des matériaux cimentaires dans l'environnement du stockage de déchets radioactifs. Toutefois, dans l'état actuel, la base de données ne propose que des données thermodynamiques sur les phases cimentaires bien cristallisées, ainsi que sur un jeu de données limité à trois compositions chimiques différentes pour les C-S-H nanocristallins, ne permettant pas de reproduire la dégradation des matériaux cimentaires, ni de modéliser la dégradation des nouvelles formulations telles que les bétons "bas-pH".L'objectif est donc d'acquérir un jeu de données thermodynamiques complémentaire, sur les phases telles que les C-S-H (Silicates de Calcium Hydratés), C-A-S-H (Silicates de Calcium Alumineux Hydratés) et M-S-H (Silicates de Magnésium Hydratés), pour les intégrer à la base de données Thermo-Chimie. Cette étude s'appuie sur un travail expérimental, analytique et numérique dans le but d'obtenir un jeu de données thermodynamiques (ΔfG0, ΔfH0, Cp(T), S0) suffisamment représentatif de la variabilité chimiques de ce type de phases. Enfin, cet ensemble de donnée permet le développement d'un modèle de prédiction de données thermodynamiques dans des espaces de compositions et de températures étendues.Le développement de ce modèle de prédiction requiert (i) l'acquisition de propriétés thermodynamiques sur des phases représentatives du système chimique étudié, et (ii) une connaissance précise de la structure et des formules chimiques de ces phases. Trois types d'hydrates ont donc été synthétisés puis caractérisés : les C-S-H, les C-A-S-H et les M-S-H. Des méthodes analytiques telles que la DRX, l’ATG et la RMN du solide (29Si, 27Al) permettent d'établir des similitudes entre la structure des C-(A-)S-H et celle de la tobermorite d'une part, et entre la structure des M-S-H et celle des phyllosilicates Mg-Si 2:1 d'autre part. Les hydrates présentent toutefois une nanocristallinité ainsi que des défauts tant au niveau de la polymérisation du silicium tétraédrique qu'au niveau de l'empilement de leurs feuillets.Une approche multi-techniques est également utilisée, couplant isothermes d'adsorption (eau et azote) et RMN 1H aux résultats de DRX et ATG, pour discriminer les différents types d'eau plus ou moins liés à la structure des C-(A-)S-H. Cette étude a permis de mettre en évidence et de quantifier les différents types d'eau composant la structure des C-(A-)S-H. L'impact des méthodes de préparation a également été mis en évidence sur la quantification des différents types d'eau et notamment l'eau interfoliaire. L'acquisition des paramètres thermodynamiques sur les phases synthétisées est réalisée à partir de l'analyse des solutions d'équilibre pour le calcul des log K et ΔfG0, alors que des acquisitions calorimétriques permettent l'obtention des capacités calorifiques ainsi que le calcul de S0. Enfin, l'enthalpie de formation de ces phases est calculée à partir des enthalpies libres et des entropies. Le modèle de prédiction des données thermodynamiques est développé sur la base des propriétés acquises... / Concrete is one of the most widely used building materials in the world. Durability, mechanical and chemical properties have made it a material of choice in storage concepts proposed by the French National Agency for Radioactive Waste Management (Andra), including the achievement of retaining structures, cell plugs, massive supports or conditioning waste. The study of the stability of the constituent phases of cementitious materials is needed in view of the planned quantities and the durability of the structures, andmust consider (i) temperature ranges suitable for cement matrices containment in contact with exothermic waste (25-80°C), and (ii) a representative time scale of the lifetime of the storage.The Andra ThermoChimie project therefore aims to develop a consistent thermodynamic database, to model the chemical evolution of cement materials in the environment of radioactive waste. However, in the present state, the database offers only thermodynamic data of cementitious crystalline phases, as well as a limited data set of three different chemical compositions for nanocrystalline C-S-H. This does not allow to reproduce the degradation of cementitious materials, or model the degradation of the new formulations, such as "Low pH" concretes.The objective is therefore to acquire a thermodynamic complementary data set on phases such as C-S-H (Calcium Silicate Hydrates) C-A-S-H (Calcium Aluminate Silicate Hydrates) and M-S-H (Magnesium Silicate Hydrates), to complete the ThermoChimie database. This study is based on experimental, analytical and digital work, in order to obtain a set of thermodynamic data (ΔfG0, ΔfH0, Cp(T), S0) sufficiently representative of the chemical variability of these phases. Finally, this set of data allows the development of a thermodynamic predictive model in extended spaces of compositions and temperatures.Development of this predictive model requires (i) The acquisition of thermodynamic properties on representative phases of the studied chemical system, and (ii) a precise knowledge of the structure and chemical formulas of these phases. Three types of hydrates were therefore synthesized and characterized: C-S-H, C-A-S-H and M-S-H. Analytical methods such as XRD, TGA and solid state NMR (29Si, 27Al) are used to ascertain similarities between the structure of C-(A-)S-H and that of tobermorite, and between the structure of M-S-H and that of Mg-Si phyllosilicates 2:1. Hydrates, however, have a lower crystallinity, with defects in the polymerization of silica chains, and random stacking faults (turbostratism).A multi-technique approach is also used, combining adsorption isotherm (water and nitrogen) and 1HNMR with XRDand TGA, and allows characterization of different types of water more or less bound to the structure of C-(A-)S-H.This study allowed to highlight and quantify the different types of water in the C-(A-)S-H structure. The impact of the drying process was also highlighted on the quantification of different types of water, including interlayer water. The acquisition of thermodynamic parameters of the synthesized phases is carried out from the analysis of equilibrium solutions for the calculation of log K and ΔfG0, while calorimetric acquisitions permit obtaining heat capacities and the calculation of S0. Finally, enthalpy of formation of these phases is calculated from the Gibbs free energy of formation and entropies.The predictive model is developed fromthe acquired thermodynamic properties.The Gibbs free energy of formation ΔfG0 is predicted from an electronegativity model, while Cp and S0 are predicted through polyhedral decomposition model. Finally, a comparison of data obtained with those published in the literature, and the realization of predominance diagrams generalized to the whole CaO-MgO-Al2O3-SiO2-H2O system assess the reliability of the proposed model.

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Cette thèse présente les mesures et l'analyse thermodynamique d'équilibres de phases de systèmes d'hydrates contenant du dioxyde de carbone (CO2), dans le contexte de procédés alternatifs de captage du CO2. Le développement de nouveaux procédés de séparation par voie de cristallisation par hydrates est un point crucial de cette thématique. Les conditions de température et de pression requises et l'utilisation de promoteurs thermodynamiques sont au-delà des opérations habituelles et des bases de données existantes. La connaissance précise des conditions de formation et dissociation d'hydrates de gaz en présence d'additifs chimiques constitue une contrainte importante d'un point de vue thermodynamique et est nécessaire pour la modélisation et l'établissement de la faisabilité de nouveaux procédés industriels impliquant des hydrates de gaz. Dans cette thèse, nous présentons un nouveau dispositif expérimental qui combine techniques statiques et techniques analytiques, ce dernier a été spécialement développé pour mesurer des données d'équilibres des phases hydrate-liquide-gaz à des températures variant entre 233 et 373 K et à des pressions jusqu' à 60 MPa. De nouvelles données d'équilibre de phases des systèmes (CO2 + méthane), (CO2 + azote) et (CO2 + hydrogène) ont été mesurées dans des conditions de formation d'hydrates en suivant la méthode isochorique avec variation de la pression en fonction de la température, et en analysant la composition en phase gazeuse. Les données d'équilibre et les conditions de dissociation d'hydrates générées dans ce travail sont comparées avec les données de la littérature. La fiabilité des modèles thermodynamiques les plus couramment utilisés est aussi étudiée. Les comparaisons entre les données expérimentales et prédites de dissociation d'hydrates suggèrent la nécessité de réajuster les paramètres des modèles thermodynamiques pour les systèmes contenant des hydrates de CO2. En outre, l'effet promoteur du bromure de tetrabutylammonium (TBAB) sur les équilibres des phases des gaz purs et de mélanges contenant du CO2 a été étudié. L'effet le plus important de promotion (réduction de la pression de formation des hydrates > 90%) est observé pour le système (TBAB + azote). Les résultats expérimentaux suggèrent que le CO2 peut être séparé de mélanges de gaz industriels ou de combustion à des températures douces et à de basses pressions à l'aide de TBAB en tant que promoteur thermodynamique. La pression requise pour la formation d'hydrates à partir de mélanges de (CO2 + azote) est réduite de 60 % en présence de TBAB. / This thesis addresses the measurement and thermodynamic analysis of the phase equilibrium behavior of carbon dioxide (CO2) hydrate-forming systems in the context of alternative capture engineering approaches. The development of new technologies based on gas hydrates requires specific temperature and pressure conditions and the utilization of thermodynamic promoters that are beyond usual operations and existing databases. Accurate knowledge of gas hydrates formation and dissociation from thermodynamics point of view in the presence of chemical additives is necessary for modeling purposes and to establish the feasibility of emerging industrial processes involving gas hydrates. In this thesis, a new experimental set-up and method for measuring pressure, temperature and compositional phase equilibrium data of high accuracy are presented. The equipment is based on the ‘static-analytic' technique with gas phase capillary sampling and it is suitable for measurements in a wide temperature range (i.e. 233 to 373 K) and pressures up to 60 MPa. New phase equilibrium data in the (CO2 + methane), (CO2 + nitrogen) and (CO2 + hydrogen) systems under hydrate formation conditions were measured following an isochoric pressure-search method in combination with gas phase compositional analysis. The equilibrium data generated in this work are compared with literature data and also with the predictions of two thermodynamic literature models. Comparisons between experimental and predicted hydrate dissociation data suggest a need of readjusting model parameters for CO2 hydrate-forming systems. In addition, the thermodynamic stability of Tetra-n-Butyl Ammonium Bromide (TBAB) semi-clathrates (sc) with pure and mixed gases was investigated. The largest promotion effect (> 90% reduction in hydrate formation pressure) is observed for (TBAB + nitrogen) sc. The experimental results suggest that CO2 can be separated from highly to low concentrated industrial/flue gas mixtures at mild temperatures and low pressures by using TBAB as thermodynamic promoter. The pressure required for hydrate formation from (CO2 + nitrogen) gas mixtures is reduced by 60% in the presence of TBAB.

Basische Magnesiumsalz-Hydrate, insbesondere die Chloride, stellen die Bindemittelphasen des Magnesiabaustoffs (auch Sorelbaustoff genannt) dar. Eine besondere Anwendung findet dieser Baustoff aufgrund seiner empirisch bekannten Beständigkeit gegenüber Salz bzw. salzhaltigen Lösungen zur Errichtung geotechnischer Barrieren in tiefen geologischen Formationen des Salinars. Die Bewertung der Langzeitbeständigkeit von Sorel-basierten Baustoffen in salinarer Umgebung erfordert Kenntnisse zu den Löslichkeitsgleichgewichten ausgehend vom ternären Grundsystem Mg(OH)2-MgCl2-H2O bis hin zu komplexeren Systemen bei NaCl-Sättigung und Anwesenheit von Sulfaten. Zielstellung dieser Arbeit war daher die experimentelle Bestimmung von Löslichkeitsdaten basischer Magnesiumchlorid- und Magnesiumsulfat-Hydrate im Temperaturbereich von 25 °C bis 120 °C. Der Einfluss von NaCl-Sättigung auf die Löslichkeit der basischen Magnesiumchlorid-Hydrate wurde im quaternären System Na+, Mg2+ / Cl-, OH- // H2O bei 25 °C untersucht. Anhand dieser Ergebnisse wurden PITZER-Parameter angepasst und erstellt, um thermodynamische Modellierungen auf Basis des Aktivitätskoeffizientenmodells nach PITZER für diese Systeme durchführen zu können.

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