Hydrate film growth has been examined at the hydrocarbon/water interface for cyclopentane and methane hydrate. Video microscopy was used to measure hydrate film thickness, propagation rate across the hydrocarbon/water interface and gas consumption measurements characterized the hydrate formation mechanism. Cyclopentane and methane hydrate film formation were measured over the temperature range of 260–279K and pressure range of atmospheric to 8.3MPa. Hydrate formation was initiated by the propagation of a thin, porous film across the hydrocarbon/water interface. The propagation rate and thickening of the hydrate film was strongly dependent on the hydrate former solubility in the aqueous phase, in the absence and presence of hydrate. Cyclopentane hydrate film thickness began at ~12 μm and grew to a final thickness (15–40 μm) which increased with subcooling. Methane hydrate film thickness began at ~ 5 μm and grew to a final thickness (20–100 μm) which also increased with subcooling. The hydrate film grew into the water phase. Gas consumption measurements indicated that the aqueous phase supplied hydrate former during the initial hydrate growth, and the free gas supplied the hydrate former for film thickening and development. Hydrate film formation at the hydrocarbon/water interface was proposed to consist of three consecutive stages: propagation, development and bulk conversion.

The hydrogen absorption behavior of organic-compound clathrate hydrates was investigated using five kinds of organic compounds as well as tetrahydrofuran (THF). These hydrates were pressurized by hydrogen, and Raman analysis, the determination of the amount of hydrogen and calorimetric measurement were carried out. The Raman results show that the samples investigated in this work formed binary clathrate hydrate of hydrogen and each organic compound. The organic-compound clathrate hydrates presented similar performances to that of THF clathrate hydrate regarding hydrogen absorption and heat of dissociation. These results suggested that the organic compounds investigated in this work may become alternatives to THF.

La disparition attendue des combustibles fossiles dans un avenir proche est l'un des grands défis de ce siècle auquel nous devons faire face. Pour cela, il serait judicieux de transférer l’énergie primaire utilisée aujourd'hui en énergies renouvelables. Le secteur des transports est l'un des plus concernés par cette problématique. Une application dans ce secteur nécessite de nombreux travaux de recherche et c'est dans ce contexte que le stockage de l'hydrogène à l'intérieur des clathrate hydrates a été entrepris au cours de mon programme de recherche doctoral. Cette étude avait pour objectif d’étudier les interactions hôte-invité (dynamique) dans les clathrates hydrates et s’est étendue de la synthèse de clathrates hydrates jusque l’insertion de l'hydrogène en leur sein. Cette étude a été faite à la fois d’un point de vue expérimental et théorique : des simulations de Dynamique Moléculaire (MD) ont été utilisées afin de guider l’interprétation d’expériences de Diffusion incohérente Quasi Elastique des Neutrons (QENS). Dans un premier temps, nous avons développé cette approche méthodologique en étudiant la dynamique du clathrate hydrate de bromométhane, système prototype. Dans un deuxième temps, nous avons appliqué cette approche multi-technique à l'étude de clathrate hydrates impliqués dans la problématique du stockage d'hydrogène. Pour cela, nous avons étudié le clathrate hydrate de tétrahydrofurane (THF), utilisé comme sous-structure hôte au stockage d'hydrogène. Un dispositif expérimental original a été développé pour la préparation d'un hydrate clathrate binaires H2-THF. L’analyse des expériences de diffusion neutronique effectuée sur ce clathrate binaire a révélé l’existence de mouvements diffusifs localisés des molécules d’hydrogène à l’intérieur des cages. / The expected disappearance of fossil fuels in the near future is one of the major challenges of this century which we need to face up and it is necessary to anticipate it. For that, it will be convenient that we have begun the primary energy transfer used today to renewable energy. The sector of transport is one of the most concerned by these renewable energies. An application in this sector would require numerous research works and it is in this context that the hydrogen storage inside the clathrate hydrates has been undertaken during my PhD. This work aimed at investigating the host-guest interactions (dynamics) of clathrate hydrates and ranged from the synthesis of clathrate hydrates to the insertion of hydrogen within them. This study has been done both from experimental and theoretical point of view. Molecular Dynamics (MD) simulations were used to guide the interpretation of incoherent Quasi-Elastic Neutron Scattering (QENS) experiments. At first, we developed a methodology combining MD and QENS to investigate the dynamics of bromomethane clathrate hydrate, a prototypical system. Having validated the multi-technique approach, the methodology has been applied to investigate clathrate hydrates involved in the hydrogen storage problematic. In this issue, the tetrahydrofuran (THF) clathrate hydrate, used as host sub-structure for storing hydrogen, has been studied. An original experimental set-up has been developed for the preparation of a binary H2-THF clathrate hydrate. The analysis of QENS experiments performed on this binary clathrate hydrate revealed the existence of localized translational motion of hydrogen molecules within the clathrate cages.

Yes / Gas hydrates, or clathrate hydrates, are solid crystalline compounds, which are formed by combination of water and gas and/or some volatile liquid molecules. Prediction of hydrate stability/dissociation/equilibrium conditions of natural gases is important in separation processes, gas storage, and in preventing blockage of gas transmission pipelines. In this study, initially, the different sets of the Kihara Potential Function Parameters, KPFP, reported in the literature were used to predict the experimental hydrate dissociation conditions of methane, ethane, propane and i-butane and mixtures of these four compounds. In most cases, however, based on these sets of KPFP, the hydrate structure cannot be predicted correctly. Consequently due to incorrect estimation of the hydrate structure, especially for natural gas mixture, the predicted hydrate dissociation conditions are found inaccurate. For overcoming this fault and by using a genetic algorithm, a new set of KPFP were optimized based on the new definition of the objective function considering hydrate structure. The results show good agreement with experimental data, both in the prediction of hydrate dissociation conditions and hydrate structure.

Capturer le CO2 est devenu un domaine de recherche important en raison principalement des forts effets de serre dont il est jugé responsable. La formation d'hydrate de gaz comme technique de séparation montre un potentiel considérable, d'une part pour sa faisabilité physique et d'autre part pour une consommation énergétique réduite. En bref, les hydrates de gaz (clathrates) sont des composés ″cages″ non-stoechiométriques, cristallins comme la glace et formés par une combinaison de molécules d'eau et de molécules hôtes convenables, à basses températures et pressions élevées. Puisque la pression exigée pour la formation d'hydrate de gaz est généralement forte, il est judicieux d'ajouter du bromure tétra-n-butylique d'ammonium (TBAB) comme promoteur de formation d'hydrate de gaz. En effet, le TBAB permet généralement de réduire la pression exigée et/ou d'augmenter la température de formation aussi que de modifier la sélectivité des cages d'hydrates au profit des molécules de CO2. TBAB participe à la formation des cages par liaisons ″hydrogène″. De tels hydrates sont nommés "semi-clathrate hydrates". Évidemment, des données d'équilibres de phase fiables et précises, des modèles thermodynamiques acceptables, et d'autres études thermodynamiques sont requises pour concevoir des procédés de séparation efficaces utilisant la technologie mentionnée ci-dessus. Dans ce but, des équilibres de phase de clathrate/semi-clathrate hydrates de de divers mélanges avec des gaz contenant CO2 (CO2 + CH4/N2/H2) ont été mesurés, ici, en présence d'eau pure et de solutions aqueuses de TBAB. La partie théorique de la thèse présente un modèle thermodynamique développé avec succès sur la base de la théorie des solutions solides de van der Waals et Platteeuw (vdW-P) associée aux équations modifiées de la détermination des constantes de Langmuir des promoteurs d'hydrates pour la représentation/prédiction des équilibres en présence de ″semi-clathrate hydrates″ de CO2, CH4, et N2. Plusieurs tests de cohérence thermodynamique basés soit sur l'équation de Gibbs-Duhem, soit sur une approche statistique ont été appliqués aux données d'équilibre de phase des systèmes de ″clathrate hydrates″ simples/mélanges afin de statuer sur leur qualité.

The dependency on fossil fuels faces resource limitations and sustainability concerns. This situation requires new strategies for greenhouse gas emission management and the development of new sources of energy. This thesis explores fundamental concepts related to carbon geological storage, including CO2-CH4 replacement in hydrate-bearing sediments. In particular it addresses the following phenomena: - Interfacial tension and contact angle in CO2-water-mineral and CH4-water-mineral systems. These data are needed to upscale pore phenomena through the sediment porous network, to define multiphase flow characteristics in enhanced gas recovery operations, and to optimize the injection and storage CO2 in geological formations. - Coupled processes and potential geomechanical implications associated to CH4-CO2 replacement in hydrate bearing sediments. Results include physical monitoring data gathered for CH4 hydrate-bearing sediments during and after CO2 injection. - Performance of cap rocks as trapping structures for CO2 injection sites. This study focuses on clay-CO2-water systems and CO2 breakthrough through highly compacted fine-grained sediments. Long term experiments help evaluate different sediments according to their vulnerability to CO2, predict the likelihood and time-scale of breakthrough, and estimate consequent CO2 leaks.

The current theoretical understanding of thermodynamics of clathrate hydrates is based on the van der Waals and Plattew (vdWP) theory developed using statistical thermodynamics approach. vdWP theory has been widely used to predict the phase equilibrium of clathrate hydrates over the decades. However, earlier studies have shown that this success could be due to the presence of a large number of parameters. In this thesis, a systematic and a rigorous analysis of vdWP theory is per-formed with the help of Monte Carlo molecular simulations for methane hydrate. The analysis revealed that long range guest-water interactions and guest-guest interactions are important, Monte Carlo integration to is superior to the spherical shell approximation for the Langmuir constant calculation and even after inclusion of all the interactions and using Monte Carlo integration for Langmuir constant, the vdWP theory still fails to regress parameters correctly. This failure of vdWP theory is attributed to the rigid water lattice approximation. To address the rigid water lattice approximation, a new method is proposed. In the proposed method, the Langmuir constant is computed in flexible water lattice, by considering the movement of water molecules. The occupancy values predicted using the proposed method are in excellent agreement with the values obtained from Monte Carlo molecular simulations for variety of hydrates, methane, ethane, carbon dioxide and tetrahydrofuran(THF) hydrates . In addition to small guest molecules like methane, ethane etc. which are mod- heled as rigid, the method is extended for large guest molecules like propane and isobutane, using configurationally bias Monte Carlo method. The phase equilib-rium and occupancy along the phase equilibrium predictions from vdWP theory are compared with the exact phase equilibrium computed from Monte Carlo molecular simulations. This comparison is done for a wide variety of hydrate systems, single hydrates , binary hydrates and quaternary hydrate. In all the cases, the vdWP theory with the flexible water lattice showed significant improvement over the rigid lattice model with significantly less absolute relative deviations in pressure. Guest-cavity interactions for hydrates are calculated using abinitio calculations. In general, these guest-cavity interaction from first principle calculations are used to develop classical force field parameters in alternative to Lorentz-Berthelot rule. In the study, comparison of guest-cavity interactions from MP2 and CCSD(T) methods revealed that less expensive MP2 method, which is generally used, is insouciant to capture the dispersion interactions accurately. These guest-cavity interactions using CCSD(T) method extrapolated to complete basis set are used to model the interaction parameters between cyclopropane and water. The potential parameters obtained from ab-initio calculations are used in the calculation of Langmuir constant using vdWP theory. Langmuir constant calculated using vdWP theory with flexible water lattice gave close agreement with the values obtained from experimental occupancy data. In addition, simulation methodology to calculate ternary hydrate phase equilibrium is extended for binary hydrates. Simulations have been successful in the prediction of sIsII and sII-sI structural transitions as observed in experiments. Predicted methane-ethane binary hydrate is also compared with the available experimental phase equilibrium data. The phase equilibrium obtained from simulations showed very good qualitative agreement with the experimental data.

Les piles à combustible (PAC) utilisant l’hydrogène comme vecteur, possèdent de bons rendements énergétiques et ne produisent aucun gaz à effet de serre. Elles se présentent donc aujourd’hui comme une solution propre et efficace. Cette alternative pourrait ainsi devenir un substitut possible aux hydrocarbures et pallier l’intermittence de certaines énergies renouvelables.Il existe différents types de PAC se distinguant principalement par la nature de l’électrolyte qui compose leur membrane échangeuse de protons. Utiliser les clathratehydrates d’acide fort comme électrolyte solide représente une alternative peu explorée à ce jour. Ces systèmes sont des solides cristallins nanoporeux constitués d’un réseau hôte de molécules d’eau formant des cavités nanométriques et encapsulant des molécules invitées.Dans le cas de clathrate hydrates d’acide fort, le confinement d’acides au sein des cages aqueuses génère des excès de protons délocalisés le long de leur réseau aqueux. A température ambiante, ces clathrate hydrates présentent alors une excellente conductivité protonique, plus élevée que celle des membranes de PACs actuellement utilisées. L’objectif de ce doctorat a été d’élaborer un électrolyte à base de clathrate hydrate d’acide hexafluorophosphorique (un des meilleurs conducteurs connus de cette classe de systèmes)sur la base d’une approche physico-chimique fondamentale, et de développer un montage miniaturisé de PAC intégrant ce nouvel électrolyte.A un niveau fondamental, il a été nécessaire de comprendre les facteurs régissant la conductivité protonique élevée de ces systèmes et en particulier, le lien existant entre la conductivité et le nombre d’hydratation (rapport molaire eau/acide dans le clathrate). Les mécanismes microscopiques mis en jeu ont été étudiés en s’appuyant sur la spectroscopie et l’imagerie Raman, complétées par des expériences de résonance magnétique nucléaire, de diffraction des rayons X et de spectroscopie d’impédance électrochimique. Un ensemble d’informations structurales (type de clathrate formé, transition de phase et stabilité thermodynamique), dynamiques (modes de vibration, diffusion des protons et cinétique) et chimiques (inclusion d’impuretés fluorées) a ainsi été obtenu. En tant que sonde sélective et locale, la technique de diffusion Raman a apporté des informations uniques. Elle a permis de sonder les interactions acides-cages, de proposer un protocole expérimental permettant de contrôler le nombre d’hydratation et également, de révéler pour la première fois une microstructuration du clathrate hydrate observée uniquement au-dessus d’un seuil d’hydratation. Ces propriétés physico-chimiques ont été corrélées aux mesures de conductivité, permettant de comprendre l’impact du nombre d’hydratation et des impuretés chimiques sur les performances de l’électrolyte solide. L’ensemble de ces résultats a permis d’aboutir à un développement technologique original. Une nouvelle micropile à combustible utilisant des clathrate hydrates d’acide hexafluorophosphorique comme électrolyte a été conçue. Ce développement offre ainsi une PAC aux performances comparables aux PACs actuellement disponibles et fonctionnant de la température ambiante à des températures négatives. / Fuel cells (FC) using hydrogen possess very good energy performance and produce no greenhouse gases. It presents itself today as a clean and efficient solution. This alternative could then become a possible substitute for fossil fuels and palliate for the intermittency ofcertain renewable energies.There are various types of FC, mainly distinguished by the nature of the electrolyte that composes their proton exchange membrane. Using strong acid clathrate hydrates as solid electrolyte represents an alternative for which very little is known nowadays. These systems are nanoporous crystalline solids consisting of a water host network forming nanometric cavities encapsulating guest molecules. In the case of strong acid clathrate hydrates, the confinement of acidic species within the aqueous cages generates proton excess that isdelocalized along their aqueous network. At room temperature, these clathrate hydrates have then excellent proton conductivity, which is higher than that of the FCs membranes currently used. The objective of this PhD was to develop an electrolyte based on hexafluorophosphoricacid clathrate hydrate (one of the best-known conductors of this class of system) on the basisof a fundamental physico-chemical approach, and to develop a miniaturized FC assemblyincorporating this new electrolyte.At a fundamental level, it was necessary to understand the driving factors responsible for the super-protonic conductivity of these systems and in particular, the relationship between the conductivity and the hydration number (i.e. water to acid molar ratio in the clathrate). The microscopic mechanisms have been studied by means of Raman spectroscopy and imaging, supplemented by nuclear magnetic resonance, X-ray diffraction and electrochemical impedance spectroscopy experiments. A set of results concerning the structure (clathrate type, phase transition and thermodynamic stability), the dynamics (vibrational modes, proton diffusion and kinetics) and the chemistry (inclusion of fluorinated impurities) has thus been obtained. As a selective and microscopic probe, the Raman scattering technique provided unique information. It allowed to probe the acid-cages interactions, to propose an experimental protocol monitoring the hydration number and also,to reveal, for the first time, a microstructuration of the clathrate hydrate only observed abovea hydration threshold. These physico-chemical properties have been correlated with the conductivity measurements, making it possible to understand the impact of the hydration number and of the chemical impurities onto the electrochemical performances of the solid electrolyte. All these results led to an original technological development. A new micro-fuel cell using hexafluorophosphoric acid hydrates as the electrolyte has been designed. This development offers a FC with performances comparable to the FCs currently available and operating from room temperature to negative temperatures.