Recently, carbon dioxide injection into deep sea sediments has become one of the carbon dioxide mitigation methods since carbon dioxide hydrates are stable at the prevailing pressure and temperature conditions. The Black Sea, which is one of the major identified natural methane hydrate regions of the world, can be a good candidate for carbon dioxide storage in hydrate form. Injected carbon dioxide under the methane hydrate stability region will be in contact with methane hydrate which should be analyzed thoroughly in order to increase our understanding on the gaseous carbon dioxide and methane hydrate interaction. For the storage of huge amounts of CO2, geological structure must contain an impermeable barrier. In general such a barrier may consist of clay or salt. In this study, sealing efficiency of methane hydrate and long term fate of the CO2 disposal under the methane hydrate zone is investigated. In order to determine the interaction of CO2 and CH4 hydrate and the sealing efficiency of CH4 hydrate, experimental setup is prepared and various tests are performed including the CH4 hydrate formation in both bulk conditions and within sand particles, measurement of the permeability of unconsolidated sand particles that includes 30% and 50% methane hydrate saturations and injection of CO2 into the CH4 hydrate. Results of the experiments indicate that, presence of hydrate sharply decreases the permeability of the unconsolidated sand system and systems with hydrate saturations greater than 50% may act as an impermeable layer. Also, CO2-CH4 swap within the hydrate cages is observed at different experimental conditions. As a result of this study, it can be concluded that methane hydrate stability region in deep sea sediments would be a good alternative for the safe storage of CO2. Therefore, methane hydrate stability region in the Black Sea sediments can be considered for the disposal of CO2.

Lors du transport ou du traitement des effluents pétroliers, on peut observer la cristallisation de particules solides formées à partir d'eau et d'hydrocarbures gazeux : Les hydrates de gaz. Leur formation peut être évitée par ajout d'alcools ou de sels qui déplacent la température de formation (mais qui posent des problèmes de recyclage et de coût compte tenu des quantités utilisées) ou de faibles quantités de polymères qui bloqueraient les mécanismes de cristallisation. Afin d'étudier l'influence des additifs, nous avons développé un appareillage original permettant de mesurer in situ la turbidité d'une suspension de particules dans un réacteur pressurisé. A partir de cette mesure et de la connaissance de l'indice de réfraction des particules, il est possible de calculer la distribution en taille au moyen d'outils mathématiques que nous présentons. Nous donnons également une méthode de calcul théorique de l'indice de réfraction des hydrates de gaz que nous validons expérimentalement avec les hydrates de méthane. Nous étudions ensuite la formation des hydrates de méthane dans un réacteur agité semi fermé de deux litres à partir d'eau liquide et de méthane gazeux. La gamme de température est [0-2°C], la gamme de pression est 30-100 bars et la gamme de vitesse d'agitation est [0-600 rpm]. nous proposons une étude expérimentale du suivi de la vitesse d'absorption du gaz dans le liquide, de la période de latence précédant la formation des premiers cristaux puis de la taille et du nombre des particules en fonction de la pression et de la vitesse d'agitation. Nous étudions également l'influence de l'ajout d'additifs tels que le sable, le chlorure de potassium ou d'un surfactant tel que la polyvinylpyrrolydonne. Nous proposons ensuite une modélisation des mécanismes de cristallisation prenant en compte la germination, la croissance, l'agglomération et la flottaison des particules. Nous validons ce modèle à partir des resultats expérimentaux concernant l'influence complexe de la vitesse d'agitation. À partir des conclusions du modèle, nous examinons ensuite l'influence des additifs.

Gas hydrate consists of guest gas molecules encaged in water molecules. Methane is the most common guest molecule in natural hydrates. Methane hydrate forms under high fluid pressure and low temperature and is found in marine sediments or in permafrost region. Methane hydrate can be an energy resource (world reserves are estimated in 20,000 trillion m3 of CH4), contribute to global warming, or cause seafloor instability. Research documented in this thesis starts with an investigation of hydrate formation and growth in the pores, and the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation. Then, emphasis is placed on identifying the advantages and limitations of different gas production strategies with emphasis on a detailed study of CH4-CO2 exchange as a unique alternative to recover CH4 gas while sequestering CO2. The research methodology combines experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes.

One of the new approaches for capturing carbon dioxide from treated flue gas (post-combustion capture) and fuel gas (pre-combustion capture) is based on gas hydrate crystallization. The presence of small amount of tetrahydrofuran (THF) substantially reduces the hydrate formation pressure from a flue (CO2/N2) gas mixture and offers the possibility to capture CO2 at medium pressures [1]. A conceptual flow sheet for a medium pressure hydrate process for pre-combustion capture from a fuel gas (CO2/H2) was also developed and presented. In order to test the hydrate-based separation processes for pre and post combustion capture of CO2 at a larger scale a new apparatus that can operate with different gas/water contact modes is set up and presented.

In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually be a commercial resource yet technical and economic hurdles have historically made gas hydrate development a distant goal rather than a near-term possibility. This view began to change over the past five years with the realization that this unconventional resource could be developed in conjunction with conventional gas fields. The most significant development was gas hydrate production testing conducted at the Mallik site in Canada’s Mackenzie Delta in 2002. The Mallik 2002 Gas Hydrate Production Research Well Program yielded the first modern, fully integrated field study and production test of a natural gas hydrate accumulation. More recently, BP Exploration (Alaska) Inc. with the U.S. Department of Energy and the U.S. Geological Survey have successfully cored, logged, and tested a gas hydrate accumulation on the North Slope of Alaska know as the Mount Elbert Prospect. The Mallik 2002 project along with the Mount Elbert effort has for the first time allowed the rational assessment of the production response of a gas hydrate accumulation.

The presence of gas hydrates offshore of eastern Canada has long been inferred from estimated stability zone calculations, but the physical evidence is yet to be discovered. While geophysical evidence derived from seismic and borehole logging data provides indications of hydrate occurrence in a number of areas, the results are not regionally comprehensive and, in some cases, are inconsistent. In this study, the results of systematic seismic mapping along the Scotian and Newfoundland margins are documented. An extensive set of 2-D and 3-D, single and multi-channel, seismic reflection data comprising ~45,000 line-km was analyzed for possible evidence of hydrate. Bottom simulating reflectors (including one double BSR) were identified at five different sites, ranging between 300 and 600 m below the seafloor and in water depths of 1000 to 2900 m. The combined area of the five BSRs is 1720 km2, which comprises a small proportion of the theoretical stability zone area along the Scotian and Newfoundland margins (~635,000 km2). The apparent paucity of BSRs may relate to the rarity of gas hydrates on the margin or may be simply due to geophysical limitations in detecting hydrate.

Geochemical processes associated with gas hydrate formation lead to the growth of iron sulphides which have a geophysically-measurable magnetic signature. Detailed magnetic investigation, complemented by petrological observations, were undertaken on cores from a permafrost setting, the Mackenzie Delta (Canadian Northwest Territories) Mallik region, and two marine settings, IODP Expedition 311 cores from the Cascadia margin off Vancouver Island and the Indian National Gas Hydrate Program Expedition 1 from the Bengal Fan. Stratigraphic profiles of the fine scale variations in bulk magnetic measurements correspond to changes in lithology, grain size and pore fluid geochemistry which can be correlated on local to regional scales. The lowest values of magnetic susceptibility are observed where iron has been reduced to paramagnetic pyrite, formed in settings with high methane and sulphate or sulphide flux, such as at methane vents. High magnetic susceptibility values are observed in sediments which contain detrital magnetite, for example from glacial deposits, which has survived diagenesis. Other high magnetic susceptibility values are observed in sediments in which the ferrimagnetic iron-sulphide minerals greigite or smythite have been diagenetically introduced. These minerals are mostly found outside the sediments which host gas hydrate. The mineral textures and compositions indicate rapid disequilibrium crystallization. The unique physical and geochemical properties of the environments where gas hydrates form, including the availability of methane to fuel microbiological activity and the concentration of pore water solutes during gas hydrate formation, lead to iron sulphide precipitation from solute-rich brines. Magnetic surveying techniques help delineate anomalies related to gas hydrate deposits and the diagenesis of magnetic iron minerals related to their formation. Detailed core logging measurements and laboratory analyses of magnetic properties provide direct ties to original lithology, petrophysical properties and diagenesis caused by gas hydrate formation.

Seismic reflection data from a multi-channel streamer deployed offshore Korea reveal evidence of hydrateforming gases being vented into the ocean. Numerous, localised vent structures are apparent from reduced seismic reflection amplitude, high seismic velocities, and reflector pull-up. These structures penetrate upward from the base of the gas hydrate stability zone (GHSZ) and are typically several hundred metres wide, and only a few hundred metres high. Underlying zones of reduced reflection amplitude and low velocities indicate the presence of gas many kilometers below the seabed, which migrates upward through near-vertical conduits to feed the vent structures. Where the local geology and underlying plumbing indicates a high flux of gases migrating through the system, the associated vent structures show the greatest change of reflector pull-up (the greatest concentration of hydrate) to be near the seabed; where the local geology and underlying plumbing indicates a moderate flux of gases, the greatest change of reflector pullup (the greatest concentration of hydrate) is near the base of the GHSZ. The distribution of gas hydrate in the high-flux gas vent is consistent with the recent salinity-driven model developed for a rapid and continuous flow of migrating gas, while the hydrate distribution in the lower-flux vent is consistent with a liquid-dominated system. The high-flux vent shows evidence of recent activity at the seabed, and it is likely that a substantial amount of gas is passing, or has passed, through this vent structure directly into the overlying ocean.

Formations containing gas hydrates are encountered both during ocean drilling for oil or gas, as well as gas hydrate exploration and exploitation. Because the formations are usually permeable porous media, inevitably there are energy and mass exchanges between the water-based drilling fluids and gas hydrates-bearing formation during drilling, which will affect the borehole’s stability and safety. The energy exchange is mainly heat transfer and gas hydrate dissociation as result of it. The gas hydrates around the borehole will be heated to decomposition when the drilling fluids’ temperature is higher than the gas hydrates-bearing formation in situ. while mass exchange is mainly displacement invasion. In conditions of close-balanced or over-balanced drilling, the interaction between drilling fluids and hydrate-bearing formation mainly embodies the invasion of drilling fluids induced by pressure difference and hydrate dissociation induced by heat conduction resulting from differential temperatures. Actually the invasion process is a coupling process of hydrate dissociation, heat conduction and fluid displacement. They interact with each other and influence the parameters of formation surrounding the borehole such as intrinsic mechanics, pore pressure, capillary pressure, water and gas saturation, wave velocity and resistivity. Therefore, the characteristics of the drilling fluids invading into the hydrate-bearing formation and its influence rule should be thoroughly understood when analyzing on wellbore stability, well logging response and formation damage evaluation of hydrate-bearing formation. It can be realized by establishing numerical model of invasion coupled with hydrate dissociation. On the assumption that hydrate is a portion of pore fluids and its dissociation is a continuous water and gas source with no uniform strength, a basic mathematical model is built and can be used to describe the dynamic process of drilling fluids invasion by coupling Kamath’s kinetic equation of heated hydrate dissociation into mass conservation equations.

Discovery of natural methane hydrate in deepwater sediments in the east-coast of India have generated significant interest in recent times. This work puts forward a possible relationship of multi-TCF gas accumulation through destabilization of paleo-hydrate in Plio-Pleistocene deepwater channel sands of Krishna-Godavari basin, India. Analysis of gas in the study area establishes its biogenic nature, accumulation of which is difficult to explain using the elements of conventional petroleum system. Gas generated in sediments by methanogenesis is mostly lost to the environment, can however be retained as hydrate under suitable conditions. Longer the time a layer stayed within the gas hydrate stability zone (GHSZ) greater is the chance of retaining the gas which can be later released by change in P-T conditions due to sediment burial. P-T history for selected stratigraphic units from each well is extracted using 1-D burial history model and analyzed. Hydrate stability curves for individual units through time are generated and overlain in P-T space. It transpired that hydrate formation and destabilization in reservoir units of same stratigraphic level in different wells varies both in space and time. Presence of paleo hydrates is confirmed by the occurrence of authigenic carbonate cement and low-saline formation water. We demonstrate how gas released by hydrate destabilization in areas located at greater water depths migrates laterally and updip along the same stratigraphic level to be entrapped in reservoirs which is outside the GHSZ. In areas with isolated reservoirs with poor lateral connectivity, the released gas may remain trapped if impermeable shale is overlain before the destabilization of hydrate. The sequence of geological events which might have worked together to form this gas reservoir is: deposition of organic rich sediments → methanogenesis → gas hydrate formation → destabilization of hydrate and release of gas → migration and entrapment in reservoirs.