[pt] Escoamentos bifásicos no regime anular são caracterizados pela formação de um filme de líquido ao redor das paredes do duto com a fase gasosa escoando na área central do duto. O presente trabalho consiste na simulação numérica de um escoamento anular em tubulação horizontal, com e sem transferência de calor através de um código unidimensional baseado no Modelo de Dois Fluidos. São considerados dois pares de fluidos, sendo o primeiro ar-água, o qual é vastamente estudado na literatura e um fluido típico encontrado na produção de petróleo formado de gás natural e óleo. Parâmetros característicos do padrão de escoamento anular como gradiente de pressão, fator de atrito da interface e espessura do filme de líquido são determinados e comparados com dados experimentais e numéricos, apresentando boa concordância. O gás natural é modelado como gás real, através da aplicação da Equação de Estado de Peng-Robinson e comparado com a modelagem utilizando Equação de Gases Ideais. Para o fluido típico selecionado, este efeito é muito pequeno tanto com relação aos parâmetros hidrodinâmicos como velocidades das fases e queda de pressão como nos parâmetros térmicos como campo de temperatura, perda de calor para o ambiente e coeficiente bifásico de troca de calor. / [en] Annular two-phase flow is characterized by the formation of a liquid layer spread around the pipe circumference with gas flowing in the core area of the pipe. The present work consists in the numerical simulation of an annular flow in horizontal pipe, with and without heat transfer through a one-dimensional code based on the Two Fluid Model. Two pairs of fluids are considered, being the first air-water, which is widely studied in the literature and a typical natural gas and oil fluid from production oil fields. Characteristics parameters of annular flow such as pressure drop, interface friction factor e liquid film height are obtained and compared with experimental and numerical data, showing in both cases good agreement. The natural gas is modeled as real gas, using the Peng-Robinson Equation of State, and compared with the ideal gas modeling. For the typical fluid selected, this effect is quite small on the hydrodynamics parameters such as phases velocities and pressure drop and on the thermal parameters such as temperature, heat loss for the environment and heat exchange coefficient.

Nous étudions le modèle O (N) relativiste, une généralisation quantique de la théorie φ⁴ utilisée en physique statistique pour étudier des transitions de phase. Ce modèle décrit certaines transitions de phase quantiques telles que la transition isolant de Mott-superfluide dans un gaz de bosons piégés dans un réseau optique ou la transition paramagnétique-antiferromagnétique dans un aimant. En deux dimensions d’espace, ces systèmes sont fortement corrélés près de la transition. Nous les étudions à l’aide du groupe de renormalisation non perturbatif, une formulation du groupe de renormalisation de Wilson. Nous nous intéressons aux propriétés universelles au voisinage de la transition de phase quantique à température nulle. Ainsi, nous déterminons les fonctions d’échelle universelles qui définissent la thermodynamique et démontrons que ces fonctions sont reliées à celles décrivant la force de Casimir critique dans un système classique tridimensionel. Ensuite, nous étudions le spectre d’excitation dans la phase ordonnée à température nulle. Pour N = 2 et 3, nous établissons l’existence d’un mode d’amplitude aussi appelé « mode de Higgs » par analogie avec le mécanisme de Higgs en physique des hautes énergies. Pour N = 1, nous montrons l’existence d’un état lié pour des dimensions proches de trois. Enfin, nous calculons la dépendance en fréquence de la conductivité à température nulle et confirmons son universalité, en particulier à la transition. Nous établissons que l’une des composantes du tenseur de conductivité dans la phase ordonnée est une quantité « superuniverselle », ne dépendant ni de la distance au point critique ni de N. / We study the relativistic O (N) model, a quantum generalization of the φ⁴ theory used in statistical physics to study some phase transitions. This model describes quantum phase transitions such as the Mott insulator-superluid transition in boson gases trapped in optical latices or the paramagnetic-antiferromagnetic transition in magnets. In two space dimensions, these systems exhibit strong correlations near the transition. We study them using the nonperturbative renormalization group, an implementation of Wilson’s renormalization group. We focus on the universal properties in the vicinity of the zero-temperature quantum phase transition. We determine the universal scaling functions which define the thermodynamics and we show that these functions are related to those describing the critical Casimir forces in a three-dimensional system. Then, we study the excitation spectrum in the zero-temperature ordered phase. For N = 2 and 3, we establish the existence of an amplitude mode, also called “Higgs mode” by analogy with the Higgs mechanism in high-energy physics. For N = 1, we show the existence of a bound state at dimensions close to three. Finally, we compute the frequency-dependent conductivity at zero temperature and confirm its universal character, in particular at the transition. We prove that one of the components of the conductivity tensor in the ordered phase is a “superuniversal” quantity depending neither on the distance to the critical point nor on N.

A descoberta de petróleo na camada de Pré-Sal possibilita a geração de ganhos em relação à dependência energética do país, mas também grandes desafios econômicos e tecnológicos. Os custos de extração são maiores devido a vários fatores como a exigência de equipamentos de exploração que suportem elevadas pressões, altas temperaturas e grandes concentrações de gases ácidos, tais quais, dióxido de carbono (CO2) e sulfeto de hidrogênio (H2S). Uma das principais preocupações com o CO2 é evitar liberá-lo para a atmosfera durante a produção. Com a modelagem termodinâmica de dados de equilíbrio de sistemas envolvendo CO2 supercrítico e hidrocarbonetos é possível projetar equipamentos utilizados em processos de separação. A principal motivação do trabalho é o levantamento de dados de equilíbrio de fases de sistemas compostos de CO2 e hidrocarbonetos, possibilitando assim prever o comportamento dessas misturas. Os objetivos específicos são a avaliação do procedimento experimental, a estimação e predição dos parâmetros de interação binários para assim prever o comportamento de fases dos sistemas ternários envolvendo CO2 e hidrocarbonetos. Duas metodologias foram utilizadas para obtenção dos dados de equilíbrio: método estático sintético (visual) e método dinâmico analítico (recirculação das fases). Os sistemas avaliados foram: CO2 + n-hexano, CO2 + tetralina, CO2 + n-hexadecano, CO2 + n-hexano + tetralina e CO2 + tetralina + n-hexadecano à alta pressão; tetralina + n-hexadecano à baixa pressão. Para o tratamento dos dados foi utilizada equação de estado cúbica de Peng-Robinson e a regra de mistura clássica / The discovery of oil in the pre-salt layer enables the generation of earnings in relation to the energy dependence of the country, but also large economic and technological challenges. Extraction costs are higher due to various factors such as the demand for mining equipment capable of withstanding high pressures, high temperatures and high concentrations of acid gases, as such, carbon dioxide (CO2) and hydrogen sulfide (H2S). A major concern with CO2 is to avoid releasing it into the atmosphere during production. With the thermodynamic equilibrium modeling systems involving data supercritical CO2 and hydrocarbon is possible to design equipment used in separation processes. The main motivation is the data collection phase equilibrium compounds CO2 systems and hydrocarbons, thus enabling predict the behavior of these mixtures. The specific objectives are to assess the experimental procedure, the estimation and prediction of binary interaction parameters so as to predict the behavior of phases of ternary systems involving CO2 and hydrocarbons. Two methodologies were used to obtain the equilibrium data: synthetic static method (visual) and analytical dynamic method (recycling phase). The systems were evaluated: CO2 + n-hexane, CO2 + tetralin, CO2 + n-hexadecane, CO2 + n-hexane + tetralin, and CO2 + tetralin + n-hexadecane at high pressure; tetralin + n-hexadecane at low pressure. For the treatment of the data was used cubic equation of state of Peng-Robinson and the classical mixing rule

A descoberta de petróleo na camada de Pré-Sal possibilita a geração de ganhos em relação à dependência energética do país, mas também grandes desafios econômicos e tecnológicos. Os custos de extração são maiores devido a vários fatores como a exigência de equipamentos de exploração que suportem elevadas pressões, altas temperaturas e grandes concentrações de gases ácidos, tais quais, dióxido de carbono (CO2) e sulfeto de hidrogênio (H2S). Uma das principais preocupações com o CO2 é evitar liberá-lo para a atmosfera durante a produção. Com a modelagem termodinâmica de dados de equilíbrio de sistemas envolvendo CO2 supercrítico e hidrocarbonetos é possível projetar equipamentos utilizados em processos de separação. A principal motivação do trabalho é o levantamento de dados de equilíbrio de fases de sistemas compostos de CO2 e hidrocarbonetos, possibilitando assim prever o comportamento dessas misturas. Os objetivos específicos são a avaliação do procedimento experimental, a estimação e predição dos parâmetros de interação binários para assim prever o comportamento de fases dos sistemas ternários envolvendo CO2 e hidrocarbonetos. Duas metodologias foram utilizadas para obtenção dos dados de equilíbrio: método estático sintético (visual) e método dinâmico analítico (recirculação das fases). Os sistemas avaliados foram: CO2 + n-hexano, CO2 + tetralina, CO2 + n-hexadecano, CO2 + n-hexano + tetralina e CO2 + tetralina + n-hexadecano à alta pressão; tetralina + n-hexadecano à baixa pressão. Para o tratamento dos dados foi utilizada equação de estado cúbica de Peng-Robinson e a regra de mistura clássica / The discovery of oil in the pre-salt layer enables the generation of earnings in relation to the energy dependence of the country, but also large economic and technological challenges. Extraction costs are higher due to various factors such as the demand for mining equipment capable of withstanding high pressures, high temperatures and high concentrations of acid gases, as such, carbon dioxide (CO2) and hydrogen sulfide (H2S). A major concern with CO2 is to avoid releasing it into the atmosphere during production. With the thermodynamic equilibrium modeling systems involving data supercritical CO2 and hydrocarbon is possible to design equipment used in separation processes. The main motivation is the data collection phase equilibrium compounds CO2 systems and hydrocarbons, thus enabling predict the behavior of these mixtures. The specific objectives are to assess the experimental procedure, the estimation and prediction of binary interaction parameters so as to predict the behavior of phases of ternary systems involving CO2 and hydrocarbons. Two methodologies were used to obtain the equilibrium data: synthetic static method (visual) and analytical dynamic method (recycling phase). The systems were evaluated: CO2 + n-hexane, CO2 + tetralin, CO2 + n-hexadecane, CO2 + n-hexane + tetralin, and CO2 + tetralin + n-hexadecane at high pressure; tetralin + n-hexadecane at low pressure. For the treatment of the data was used cubic equation of state of Peng-Robinson and the classical mixing rule

Orientador: Martin Aznar / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-08T09:32:38Z (GMT). No. of bitstreams: 1 AlvarezAlvarez_VictorHugo_M.pdf: 1355509 bytes, checksum: c9710252adab51dca90a695fc91a5aa6 (MD5) Previous issue date: 2007 / Resumo: Os líquidos iônicos têm recebido considerável interesse devido a seu potencial como solventes projetados, que podem ser adaptados a vários tipos de processos industriais. A razão principal do interesse nos líquidos iônicos como solventes é sua baixa pressão de vapor, a qual minimiza os riscos de exposição e contaminação ambiental. Esta pesquisa visa realizar um estudo completo e sistemático sobre duas regras de mistura utilizando a equação de estado cúbica de Peng-Robinson para correlacionar o equilíbrio líquido-vapor em sistemas contendo líquidos iônicos. O problema principal nesta modelagem é a predição da baixa concentração do líquido iônico na fase vapor.Até o momento são escassas as publicações das propriedades críticas dos líquidos iônicos, motivo pelo qual escolheu-se uma equação com baixa quantidade de parâmetros, como a equação de estado cúbica de Peng-Robinson. Estudou-se o parâmetro dependente da temperatura a(T) e a regra de mistura de van der Waals. Os parâmetros a(T) comparados foram os propostos por Soave (1972) e por Almeida et al. (1991). Nos primeiros testes da modelagem foi utilizada a regra de mistura de van der Waals, mas para melhores resultados utilizou-se a regra de mistura de Wong-Sandler com os modelos UNIQUAC ou NRTL. Desenvolveu-se uma estratégia de modelagem molecular para calcular os parâmetros estruturais de área e volume do modelo UNIQUAC para os líquidos iônicos. Os parâmetros de interação foram calculados independentes da temperatura e concentração. Foram estudadas misturas binárias para descrever o equilíbrio líquido-vapor em altas pressões (CO2 ou CHF3 supercrítico + líquido iônico) e a baixas pressões (hidrocarbonetos + líquidos iônicos). Logo, os parâmetros de interação binária foram utilizados na correlação de sistemas ternários a baixa pressão com a regra de mistura de Wong-Sandler. A estimação dos parâmetros de interação binários foi realizada em um primeiro momento com o método de Levenberg-Marquardt e depois, com melhor sucesso, utilizou-se um algoritmo genético. A função objetivo utilizada contém a pressão do sistema e a composição do líquido iônico na fase gás. Os resultados para a modelagem com a regra de mistura de van der Waals apresentam altos desvios na pressão, mas com a regra de mistura de Wong-Sandler têm-se baixos desvios na pressão e uma baixa concentração do líquido iônico na fase gás até 100 atm. Os resultados mostram uma boa correlação dos sistemas ternários. Foi usado um teste de consistência termodinâmica para o sistema CO2 + hexafluorofosfato de 1-butil-3-metilimidazolio, para o qual há quatro conjuntos de dados conflitantes na literatura. Os resultados mostraram que, um conjunto de dados é termodinamicamente consistente, outro é não inteiramente consistente e os outros dois são termodinamicamente não consistentes / Abstract: The ionic liquids have received considerable interest due to his potential as designer solvents, that can be adapted in several types of industrial processes. The main reason of the interest in the ionic liquid as solvent is his negligible vapor pressure, which decreases the risks of exposition and environmental contamination. This research tries realize a complete and systematic study of two mixing rule in the Peng-Robinson equations of state for correlate and predict the equilibrium liquid-vapor in systems containing ionic liquids. The main problem in modeling the liquid-vapor equilibrium is the prediction of the negligible concentrations of ionic liquid in the phase vapor. Up to the moment the publications of the critical properties of the ionic liquids are scarce, reason for which chose an equation with low amount of parameters, as the cubic equation of state of Peng-Robinson. In this work, was studied the a(T): parameter dependent of the temperature and the mixing rule of van der Waals. The compared a(T): parameters were proposed for Soave 1972) and Almeida et al. (1991). In the first moment of the modeling was used the van der Waals mixing rule, after for good results was used the Wong-Sandler mixing rule with the UNIQUAC or NRTL model. A molecular modeling strategy was used to calculate the volume and surface area parameters of ionic liquids for UNIQUAC. Independent temperature and concentration interaction parameters were calculated. The binary mixtures were studied to describe the liquid-vapor equilibrium included high pressures (CO2 or CHF3 supercritical + ionic liquid) and low pressures (hydrocarbons + ionic liquid). After, the binary interaction parameters were used for correlated the ternary system at low pressure with the Wong-Sandler mixing rule. For evaluating the binary interaction parameters was used in first moment the Levenberg-Marquardt method and after, with best results was used a genetic algorithm. The objective function uses the pressure of the systems and the ionic liquid fraction mol in the gas phase. The results for correlation with van der Waals mixing rule show high deviations in the pressure system, but the Wong-Sandler mixing rule had low deviations in the pressure system and low concentration of the ionic liquid in the gas phase, up to 100 atm. The ternary system can be correlate with acceptable accuracy. A test of thermodynamic consistency was used for a binary system CO2 + 1-n-butyl-3-methylimidazolium hexafluorophosphate, it has four conflicts data set in the literature. The results show one data set thermodynamically consistent, one data set not fully consistent and two data set thermodynamically inconsistent / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador : Martin Aznar / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-01T10:07:01Z (GMT). No. of bitstreams: 1 Arce-Castillo_PedroFelipe_M.pdf: 13948249 bytes, checksum: 89b291cb7fd018bc32c50812717efa25 (MD5) Previous issue date: 2002 / Resumo: A modelagem e simulação de processos de extração supercrítica requer uma boa predição das condições do equilíbrio entre fases, condições que determinam a maior concentração do líquido ou sólido (soluto) a ser extraído pelo fluido supercrítico (solvente). O problema principal na modelagem dos sistemas que se encontram em processos de extração supercrítica é a grande diferença de tamanho (peso molecular) entre as substâncias envolvidas (soluto e fluido supercrítico) e a baixa concentração do soluto no fluido supercrítico. Atualmente, as regras de mistura em uso não consideram de forma adequada o problema da grande assimetria; portanto, não permitem uma boa predição do equilíbrio entre fases. É proposta uma regra de mistura (Regra Não Quadrática Generalizada) baseada nas regras de mistura clássicas de van der Waals, com modificações nos parâmetros de interação, tanto na constante de energia quanto na de volume. Um parâmetro de interação binário, dependente da concentração, é usado para estimar a constante de energia; outro parâmetro de interação binário, independente da concentração e com um efeito diferenciado sobre o componente mais pesado quando comparado ao fluido supercrítico, é usado para estimar a constante de volume. Este novo arranjo considera como casos particulares os modelos conhecidos de Panagiotopoulos-Reid e Adachi-Sugie, entre outros. A forma não quadrática generalizada proposta tem todas as boas características desses modelos, permitindo maior flexibilidade na correlação dos dados experimentais. Usou-se outra regra de mistura, Regra de Kurihara-Tochigi-Kojima, a qual está baseada na parte residual da energia livre excedente à pressão infinita, atuando diretamente sobre a constante de energia da equação de estado. Os resultados obtidos com as duas regras de misturas citadas anteriormente são comparados com os resultados obtidos da regra modificada de W ong-Sandler e da regra convencional de van der Waals. As regras de mistura descritas anteriormente, junto com as equações cúbicas de estado de Soave-Redlich-Kwong, Peng-Robinson e a equação cúbica de estado generalizada de Patel-Teja-Valderrama, são usadas para descrever o equilíbrio líquidovapor e sólido-vapor em misturas assimétricas binárias (CO2 supercritico + um componente pesado ou produto natural). Neste trabalho foram estimados os parâmetros de interação binários tanto para a modelagem do equilíbrio líquido-vapor dos sistemas binários: CO2 +limoneno, linaloo_ ac. láurico, ac. palmítico, ac. oléico, ac. linoleico, 2-metil-pentanol, 1octanol, l-decanol e a.-pineno, quanto para a modelagem do equilíbrio sólido-vapor dos sistemas binários: CO2 + naftaleno, 2,3-dimetilnaftaleno, 2,6-dimetilnaftaleno, fenantreno,antraceno, p-colesterol, cafeína, p-caroteno e capsaicina. A predição dos parâmetros de interação binários realiza-se usando um método modificado de Marquardt com uma função objetivo que contém a pressão de saturação e a concentração na fase gás para o equilíbrio líquido-vapor e apenas a concentração na fase gás para o equilíbrio sólido-vapor. As sub-rotinas computacionais foram escritas considerando a possibilidade de múltiplas soluções e conseqüentemente, a busca dos parâmetros ótimos realiza-se sob um amplio intervalo de soluções possíveis. Os resultados (desvios na pressão e na fração molar na fase vapor para o ELV e apenas os desvios na fração molar na fase vapor para o ESV) indicam que as regras de mistura NQG e WS modificada permitem predizer melhor o comportamento dos sistemas binários estudados. A influencia das EDEs para uma mesma regra de mistura não é apreciável / Abstract: Modeling and simulation of supercritical extraction processes request a good prediction of conditions of phase equilibrium, conditions that determine the higher concentration of liquid or solid (solute) to be extracted by supercritical fluid (solvent). The main problem in modeling of systems found in supercritica1 extraction processes is the great size difference (molecular weights) between involved substances (solute and supercritical fluid) and low concentration of solute in supercritical fluid. Now, mixing roles in use don't consider of appropriate way the problem of great asymmetry, therefore don't alIow a good prediction of phase equilibrium. A mixing role is proposed (Generalized Non Quadratic Rule), which is based on c1assic mixing rules of van der Waals, with modifications in the interaction parameters, as much in energy constant as in volume constant. A binary interaction parameter, dependent of concentration, is used to estimate energy constant; another binary interaction parameter, independent of concentration and with a differentiated effect on heavier component when compared with supercritical fluid, is used to estimate volume constant. This new arrangement considers as private cases well-known models of Panagiotopoulos-Reid and Adachi-Sugie among others. This generalized non quadratic form has all good characteristics of those models, allowing larger flexibility in correlating experimental data. Other mixing rule was used, Kurihara-Tochigi-Kojima Rule (based on the residual part of the excess free energy to infinite pressure), acting direct1y on energy constant of the state equation. Results obtained with the two mixing roles previously mentioned are compared with obtained results of modified role of Wong-Sandler and conventional role of van der Waals. The mixing roles described previously, joined with the Soave-Redlieh-Kwong and Peng-Robinson's cubic equations of state and the Patel-Teja-Valderrama generalized cubic equation of state, are used to describe liquid-vapor and solid-vapor equilibrium in asymmetrie binary mixtures (supercritical CO2 + heavy component or natural product). In this work were estimated the binary interaction parameters as much for the modeling of liquid-vapor equilibrium of binary systems: COz + limonene, linalool, lauric acid, palmitic acid, oleic acid, linoleic acid, 2-methyl-pentanol, l-octanol, l-decanol and a-pinene, as for modeling of solid-vapor equilibrium of the binary systems: CO2 + naphtalene, 2,3dimethylnaphtalene, 2,6-dimethylnaphtalene, phenanthrene, anthracene, B-eholesterol, caffeine, B-carotene and capsaicin. A Marquardt modified method with a objective function (saturation pressure and vapor phase concentration for liquid-vapor equilibrium and on1y vapor phase concentration for solid-vapor equilibrium) was used to predict binary interaction parameters. The computational subroutines were written considering the possibility of multiple solutions and consequently, the search of the optimum parameters was done on a large interval of possible solutions. Results (deviations in pressure and molar fraction in vapor phase for ELV and on1y deviations in fraction molar in phase vapor for ESV) indicate that mixture roles: NQG and modified WS allow to predict better the behavior of studied binary systems. The influence of EDEs for a same mixture role is not appreciable / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Dans le cadre du procédé de séparation cryogénique des gaz de l'air (T< 100 K), impuretés telles que le CO2 et le N2O peuvent se solidifier au niveau de l'échangeur de chaleur placé entre les deux colonnes de distillation cryogénique.La formation du solide doit être évitée pour deux principales raisons:- au niveau opérationnel, le solide constitue une résistance supplémentaire aux transferts de chaleur et de matière, et augmente les chutes de pression dans les colonnes de distillation;- au niveau sécurité, la présence d'une phase solide peut également favoriser l'accumulation d'hydrocarbures légers qui forment avec l'oxygène liquide des mélanges potentiellement inflammables.Les conditions de formation thermodynamique de la phase solide doivent être parfaitement maitrisées dans le cadre de la distillation cryogénique. C'est pourquoi, il est indispensable de disposer d'une équation d'état adaptée qui permette de représenter les diagrammes de phases impliquant une phase solide dans les conditions opératoire du procédé.L'objectif principal de la thèse est de développer un modèle thermodynamique pour représenter les équilibres de phases solide – fluides. Ce travail nécessite de mettre au point des algorithmes de résolution des équilibres bi et triphasiques et de déterminer le meilleur jeu de paramètres du modèle en s'appuyant sur la disponibilité des données expérimentales dans les conditions cryogéniques.Le modèle permet d'améliorer la connaissance des équilibres et constitue un outil indispensable pour maîtriser les risques associés à la présence de phases solides pour le procédé de distillation cryogénique. / In the framework of the cryogenic air separation, impurities such as CO2 and N2O may solidify at the reboiler-condenser placed between the two distillation columns.The formed solid could provide an additional strength to the heat and material transfers, and increase the pressure drops in the distillation columns.Furthermore, the presence of a solid phase can promote the accumulation of light hydrocarbons which may form flammable mixtures with liquid oxygen.Therefore, the presence of solid phases must be controlled see avoided within the cryogenic air distillation process.The main issue of this thesis is to develop a suitable model for representing solid phases and their equilibrium with the liquid and vapor phases at the operating conditions of the process, and to obtain full phase diagrams which would improve the knowledge of phase equilibria and the control of the risks associated to the presence of solid phases.

Cette thèse s’inscrit dans le cadre du projet SCRIB (“dispositif Solaire de Climatisation Réversible Intégré au Bâti”) porté par la société Helioclim. Ce projet est financé par l’état français dans le cadre des « Investissements d’avenir » pilotés par l’ADEME (Agence de l’Environnement et de la Maîtrise de l’Energie). Le but de ce projet est de développer une solution de climatisation solaire réversible capable de répondre à l’ensemble des besoins thermiques des bâtiments industriels et tertiaires (climatisation, chauffage, production de froid industriel, eau chaude sanitaire). Le système est constitué d’une machine à absorption réversible, alimentée par un système de capteurs solaires innovants. Le cycle de la machine à absorption est en configuration GAX (Generator-Absorber heat eXchange – échange de chaleur entre le générateur et l’absorbeur).Ce travail de thèse s’est intéressé au développement d’un outil logiciel aidant à la conception et au contrôle d’une telle machine. Un modèle de connaissance prenant en compte les paramètres de fonctionnement et de dimensionnement a été ainsi mis en œuvre. L’originalité de ce travail repose sur les points suivants :- L’outil logiciel propose plusieurs modules qui permettent de simuler différentes configurations de machine à absorption (mono ou multi-étagée).- Les propriétés thermodynamiques des mélanges ont été modélisées à l’aide de modèles basés sur l’utilisation d’une équation d’état ou d’un modèle d’enthalpie libre d’excès. Ainsi, le couple fluide pourra être facilement changé.- Un modèle de « Flash Positif » permet de prédire l’état de chaque courant (liquide sous-refroidi, liquide-vapeur ou vapeur surchauffée) sans poser d’hypothèses a priori. Chaque courant est considéré multiconstituant.- Les bilans matière et d’énergie sont écrits pour les différents appareils (évaporateur, absorbeur, détenteur,…).- Le générateur est modélisé par un empilement d’étages théoriques. Les équations MESH (Mass balance, Equilibrium, Summation, Heat balance) ont été écrites pour chaque étage.- Les inerties thermiques et de matière sont prises en compte.Les résultats de simulation obtenus à l’aide de cet outil logiciel ont été comparés avec succès à une étude publiée qui concernait un cycle GAX fonctionnant avec le couple ammoniac/eau. A l’aide de cet outil, le régime permanent et le comportement dynamique du système soumis à une perturbation peuvent être simulés, ce qui peut constituer une aide importante dans le développement de la politique de contrôle du système. / This PhD thesis was carried on in the framework of the SCRIB project (“dispositif Solaire de Climatisation Réversible Intégré au Bâti”) led by the Helioclim company. This project is funded by the French government (“Investissements d’Avenir” operated by the French Agency for Energy and Environment, ADEME). The goal of this project is to develop a reversible solar cooling system which can respond to a set of thermal requirements in industrial and tertiary building sector (cooling system, heating system, industrial cooling system and domestic hot water). Thus an ammonia/water absorption chiller prototype, powered by innovative thermal solar concentrators, has been built. This absorption chiller has a GAX (Generator-Absorber heat eXchange) configuration.This PhD work focused on the development of a support tool for the conception and the control of such device. A software tool has been developed implementing knowledge-based model, which took into account the operating and design parameters of the absorption chiller. The key originalities of the proposed work are as follows:- The software has been designed in a modular way allowing the simulation of various absorption chiller configurations (single or multi-stage).- The thermodynamic properties of the mixture have been modeled by equation of state or excess Gibb’s energy model. The working fluids can then be changed easily.- A “Positive Flash” model allows the description of all the possible states (sub-cooled, super-heated, biphasic…) of the various streams which are all considered as multicomponent mixtures, without a priori assumptions.- The various devices (evaporator, absorber, valves, etc.) are modeled from balance equations (mass, energy). - The generator is modeled using the concept of theoretical plates. MESH equations (Mass balance, Equilibrium, Summation, Heat balance) have been written for each stage.- Both thermal and material inertia are considered.Simulation results obtained with this software have been successfully compared to an earlier published experimental study for a GAX configuration absorption chiller which used ammonia/water as working fluids. Thanks to this tool, the steady state and the transient behavior of the system submitted to a perturbation can be simulated, which can be helpful for the development of the control policy of the absorption chiller.

Dans ce manuscrit, nous nous sommes intéressés aux propriétés des magmas ainsi qu’aux effets de l’eau sur celles-ci en utilisant la dynamique moléculaire classique. Après avoir mis en avant l’importance de l’eau dans les phénomènes géologiques et présenté quelques bases de dynamique moléculaire, nous présentons un champ de force pour les liquides silicatés anhydres. Nous utilisons ce champ de force pour étudier l’équation d’état, la structure et les propriétés de transport (viscosité, conductivité électrique, coefficient de diffusion) de liquides silicatés de composition aussi bien terrestre qu’extra-terrestre. Ces résultats sont systématiquement comparés avec les données de la littérature. Nous développons ensuite un champ de force pour l’eau pure compatible avec celui proposé pour les silicates. La validité de ce champ de force est étudiée par comparaison avec des résultats expérimentaux, de simulations ab-initio et d’autre champs de force classiques. Nous ajoutons enfin une interaction eau-silicate aux deux champs de forces précédents pour obtenir un champ de force décrivant les silicates hydratés. Celui-ci est utilisé pour étudier les propriétés des mélanges eau-silicate (solubilité, tension de surface). La structure et les propriétés des silicates hydratés sont ensuite étudiées, notamment la spéciation de l’eau, la densité, la viscosité, la conductivité électrique et les coefficients de diffusion. La structure locale autour des espèces protonées (OH-,H2O et H3O+) et leurs coefficients de diffusion sont également déterminés. Ces différents résultats sont là encore comparés aux données existantes dans la littérature. / In this manuscript, we focused on the properties of magmas and the effects of water on these properties using classical molecular dynamics simulations. After having pointed out the importance of water in geological processes and presented some basic principles of molecular dynamics simulations, we present a force field for dry silicate melts. We use this force field to study the equation of state, the structure and the transport properties (viscosity, electrical conductivity, diffusion coefficient) of silicate melts of terrestrial and extra-terrestrial compositions. These results are systematically compared with data of the literature. We then develop a force field for pure water compatible to the one proposed for silicates. The validity of this force field is investigated by comparison with experimental studies, ab-initio simulations and other MD simulations using classical force fields. At last we add a water-silicate interaction to the two former force fields in order to describe hydrous silicate melts. This force field is used to study the properties of water-silicate mixtures (solubility, surface tension). The structure and properties of hydrous silicate melts are evaluated as well as the speciation of water, the density, the viscosity, the electrical conductivity and the diffusion coefficients. The local structure around protonated species (OH-,H2O and H3O+) and their diffusion coefficients are also determined. All these results are compared with available data of the literature.

La dimensionnalité d’un système affecte fortement ses propriétés physiques ; les transitions de phasequi s’y déroulent ainsi que le type d’ordre qui y apparaît dépendent de la dimension. Dans les systèmesde basse dimension, la cohérence s’avère plus difficile à établir car les fluctuations thermiques etquantiques y jouent un rôle plus important. Le fluide de Bose à deux dimensions est particulièrementintéressant car, même si un ordre total est exclu, un ordre résiduel à « quasi-longue » portée s’établit àbasse température. Deux ingrédients ont un effet significatif sur l’état du système : (i) la taille finie d’unsystème réel permet de retrouver une occupation macroscopique d’un état à une particule ; (ii) les interactionsentre particules conduisent à l’apparition d’un type non-conventionnel de transition de phasevers un état superfluide.Dans cette thèse, nous présentons une étude expérimentale du gaz de Bose bidimensionnel (2D) utilisantdeux types de paysages énergétiques pour piéger nos atomes. Dans la première partie, nous utilisonsla dépendance spatiale de certaines propriétés locales d’un gaz inhomogène pour caractériser l’étatdu système homogène équivalent. Nous extrayons son équation d’état des profils de densité et noustestons son comportement superfluide en mesurant le chauffage induit par le mouvement d’une perturbationlocale. Dans la deuxième partie, nous observons et caractérisons l’émergence d’une cohérencede phase étendue dans un gaz 2D homogène, en particulier via le passage de trois dimensions à deux(croisement dimensionnel). Nous étudions l’établissement dynamique de la cohérence par un passagerapide du croisement dimensionnel et nous observons des défauts topologiques dans l’état superfluidefinal. Nous comparons nos résultats avec les prédictions du mécanisme de Kibble–Zurek. / The dimensionality of a system strongly affects its physical properties; the phase transitions that takeplace and the type of order that arises depend on the dimension. In low dimensional systems phasecoherence proves more difficult to achieve as both thermal and quantum fluctuations play a strongerrole. The two-dimensional Bose fluid is of particular interest as even if full order is precluded, a residual"quasi-long" range order arises at low temperatures. Then two ingredients have a significant effecton the state of the system: (i) the finite size of a real system enables one to recover of a macroscopicoccupation of a single-particle state; (ii) the interactions between particles lead to the emergence of anon-conventional type of phase transition toward a superfluid state.In this thesis, we present an experimental study of the two-dimensional (2D) Bose gas using two differentenergy landscapes to trap our atoms. In the first part, we use the spatial dependence of somelocal properties of an inhomogeneous gas to characterize the state of the equivalent homogeneous system.We extract its equation of state with a high accuracy from the gas density profiles and test itssuperfluid behavior by measuring the heating induced by a moving local perturbation. In the secondpart, we observe and characterize the emergence of an extended phase coherence in a 2D homogeneousgas in particular via a 3D-to-2D dimensional crossover. We investigate the dynamical establishment ofthe coherence via a rapid crossing of the dimensional crossover and observe topological defects in thefinal superfluid state. We compare our findings with the predictions for the Kibble–Zurek mechanism.