La cristallisation des hydrates pendant la production de pétrole est une source de risques, surtout liés au bouchage des lignes de production dû à l’agglomération des hydrates. Pendant l'extraction de pétrole, l'huile et l'eau circulent dans le pipeline et forment une émulsion instable. La phase eau se combine avec les composants d'hydrocarbures légers et peut former des hydrates. La cristallisation des hydrates a été intensivement étudiée, principalement à faible fraction d’eau. Cependant, lorsque le champ de pétrole devient mature, la fraction d’eau augmente et peut devenir la phase dominante, un système peu étudié concernant à la formation d'hydrates. Plusieurs techniques peuvent être combinées pour éviter ou remédier la formation d'hydrates. Récemment, une nouvelle classe d'additifs a commencé à être étudiée : Inhibiteurs d'Hydrates à Bas Dosage (LDHI), divisés en Inhibiteurs Cinétiques (KHI-LDHI) et anti-agglomérants (AA-LDHI).Ce travail est une étude paramétrique de la formation d'hydrates à partir de l'émulsion, en variant la fraction d’eau, le débit, en absence et en présence d’AA-LDHI. Les expériences ont été réalisées sur la boucle d'écoulement Archimède, qui est en mesure de reproduire les conditions de la mer profonde. L'objectif de cette étude est d'améliorer la compréhension de la formation d'hydrate et de comprendre comment l'additif dispersant évite l'agglomération. Pour ce faire, un modèle comportemental de la cristallisation pour les systèmes sans et avec additif a été développé. Il a également été proposé une technique pour déterminer la phase continue du système et un mécanisme d'action pour l'anti-agglomérant a été suggéré. / Crystallization of hydrates during oil production is a major source of hazards, mainly related to flow lines plugging after hydrate agglomeration. During the petroleum extraction, oil and water circulate in the flow line, forming an unstable emulsion. The water phase in combination with light hydrocarbon components can form hydrates. The crystallization of hydrates has been extensively studied, mainly at low water content systems. However, as the oil field matures, the water fraction increases and can become the dominant phase, a system less known in what concerns hydrate formation. Actually, several techniques can be combined to avoid or remediate hydrate formation. Recently, a new class of additives called Low Dosage Hydrate Inhibitor (LDHI) started to be studied, they are classified as Kinetic Hydrate Inhibitors (KHI-LDHI) and Anti-Agglomerants (AA-LDHI).This work is a parametric study about hydrate formation from emulsion systems ranging from low to high water content, where different flow rates and the anti-agglomerant presence were investigated. The experiments were performed at the Archimède flow loop, which is able to reproduce deep sea conditions. The goal of this study is enhancing the knowledge in hydrate formation and comprehending how the dispersant additive acts to avoid agglomeration. For this matter, it was developed a crystallization topological model for the systems without and with additive. A technique to determine the system continuous phase and a mechanism of the anti-agglomerant action from the chord length measurements were also proposed.

Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. The unique behavior of hydrate-bearing sediments requires the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Hydraulic conductivity decreases with increasing variance in pore size distribution; while spatial correlation in pore size reduces this trend, both variability and spatial correlation promote flow focusing. Invading gas forms a percolating path while nucleating gas forms isolated gas bubbles; as a result, relative gas conductivity is lower for gas nucleation than for gas invasion processes, and constitutive models must be properly adapted for reservoir simulations. Physical properties such as gas solubility, salinity, pore size, and mixed gas conditions affect hydrate formation and dissociation; implications include oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations. High initial hydrate saturation and high depressurization favor gas recovery efficiency during gas production from hydrate-bearing sediments. Even a small fraction of fines in otherwise clean sand sediments can cause fines migration and concentration, vuggy structure formation, and gas-driven fracture formation during gas production by depressurization.

Kinetics of hydrate formation and decomposition of methane hydrate formed in silica sand particles were studied in detail at three temperatures of 7.0, 4.0 and 1.0°C, respectively. A new apparatus was setup to study the decomposition behavior of the methane hydrate formed in the bed of silica sand particles. Six thermocouples are placed in different locations to study the temperature profiles during hydrate formation and decomposition experiments. Gas uptake measurement curves for the formation experiments and the gas release measurement curves for the decomposition experiment were determined from the experimental data. Percent conversion of water to hydrates was significantly higher for the experiments conducted at 4.0 and 1.0°C compared to 7.0°C. Recovery of methane occurred in two stages during the decomposition experiments carried out with a thermal stimulation approach at constant pressure. Methane recovery in the range of 95 to 98% was achieved.

In the present study the effect of one commercially available anionic surfactant on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. Surfactants are known to increase gas hydrate formation rate. Memory water was used and the experiments were carried out at three different degrees of undercooling and two different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. Finally, the addition of 2200 ppm of SDS was found to increase the mole consumption for hydrate formation by 4.4 times.

We have developed a one-dimensional numerical computer model (simulator) to describe methane hydrate formation, decomposition, reformation, and distribution with depth below the seafloor in the marine environment. The simulator was used to model hydrate distributions at Blake Ridge (Site 997) and Hydrate Ridge (Site 1249). The numerical models for the two sites were conditioned by matching the sulfate, chlorinity, and hydrate distribution measurements. The constrained models were then used to investigate the effect of changes in seafloor temperature and sea-level on gas hydrate stability. For Blake Ridge (site 997), changes in hydrate concentration are small. Both the changes in seafloor temperature and sea-level lead to a substantial increase in gas venting at the seafloor for Hydrate Ridge (site 1249).

Many places where natural gas hydrate occurs have a regionally extensive, bottom-simulating seismic reflector (BSR) at the base of the gas hydrate stability zone (GHSZ). This reflection marks the top of an underlying free-gas zone (FGZ). Usually, hydrate recycling (that produces gas as the stability field moves upward relative to sediments) is invoked to explain the presence and properties of the sub-BSR FGZ. However, this explanation is not always adequate: FGZs are often thicker in passive-margin environments where hydrate recycling is relatively slow, than in convergent-margin environments where hydrate recycling is relatively fast (e.g. Blake Ridge compared with Cascadia). Furthermore, some areas with thick FGZs and extensive BSRs (e.g. west Svalbard) have similar rates of hydrate recycling to northern Gulf or Mexico, yet the latter has no regional BSR. Here we discuss a gas-forming mechanism that operates in addition to hydrate recycling, and which produces a widespread, regional, BSR when gas is transported upward through the liquid phase; this mechanism is dominant in tectonically passive margins. If the gas-water solubility decreases downward beneath the GHSZ (this occurs where the geothermal gradient and the pressure are relatively high), low rates of upward fluid flow enable pore water to become saturated in a thick layer beneath the GHSZ. The FGZ that this produces achieves a steady-state thickness that is primarily sensitive to the rate of upward fluid flow. Consequently, geophysical observations that constrain the thickness of sub-BSR FGZs can be used to estimate the regional, diffuse, upward fluid flux through natural gas-hydrate systems.

The hydrogen molecule dynamics in tetrahydrofuran-H2-H2O clathrate hydrate has been studied by high-resolution inelastic neutron scattering and Raman light scattering. Several intense bands in the neutron spectrum are observed that are due to H2 molecule excitations. These are rotational transitions, center-of-mass translational transitions (rattling) of either para- or ortho-H2, and combinations of rotations and center-of-mass transitions. The rattling of the H2 molecule is a paradigmatic example of the motion of a quantum particle in a non-harmonic three-dimensional potential well. Both the H2 rotational transition and the fundamental of the rattling transition split into triplets. Raman spectra show a similar splitting of the S0(0) rotational transition, due to a significant anisotropy of the potential with respect to the orientation of the molecule in the cage. The comparison of our experimental values for the transition frequencies to a recent quantum mechanical calculation gives qualitative agreement, but shows some significant difference.

The aim of this work is to model the thermal evolution inside a hydrate forming system which is submitted to an imposed steady cooling. The study system is a cylindrical thin film of aqueous solution at 19 Mpa, the methane is the hydrate forming molecule and it is assumed that methane is homogeneously dissolved in the aqueous phase. The model in this work takes into account two factors involved in the hydrate crystallization: 1) the stochastic nature of crystallization that causes sub-cooling and 2) the heat source term due to the exothermic enthalpy of hydrate formation. The model equation is based on the resolution of the continuity equation in terms of a heat balance. The crystallization of the methane hydrate occurs at supercooling conditions (Tcryst < TF), besides, the heat released during crystallization interferes with the imposed condition of steady decrease of temperature around the system. Thus, the inclusion of the heat source term has to be considered in order to take into account the influence of crystallization. The rate of heat released during the crystallization is governed by the probability of nucleation J(T ). The results provided by the model equation subjected to boundary conditions allow depict the evolution of temperature in the dispersed phase. The most singular point in the temperature–time curve is the onset time of hydrate crystallization. Three time intervals characterize the temperature evolution during the steady cooling: (1) linear cooling, (2) hydrate formation with a release of heat, (3) a last interval of steady cooling.

How to exploit and make use of natural gas hydrates in oceans will weigh much in the future researches. Unlike the oil or gas reservoirs, the distributions of natural gas hydrate are very complicated and don’t congregate massively in oceanic sediments. Besides, factors such as seafloor geohazards and climate must be taken into account, which makes it much more difficult and complicated to exploit oceanic gas hydrates than conventional oil or gas. Nowadays neither of such methods as thermal stimulation, depressurization, inhibitor injection, carbon dioxide replacement and mixing exploitation etc. is applied to exploit gas hydrates in marine sediments because of their disadvantages. This paper introduces a conception of combining solar and geothermal energy for gas hydrates exploitation. The model mainly includes five parts: solar energy transferring module, sea water circulating module, underground boiler module, platform and gas-liquid separating module. Solar cells and electric heaters are used to heat the formations containing hydrates. Because they become relatively more mature and cheaper, it’s the key of how to utilize the geothermy to exchange heat in developing this conception, which needs solution of fluid leakage, circulating passages and heat-exchange interface problems in building underground boiler. Probably it’s a feasible measure to use an effective hydraulic control system and hydraulic fracturing. The idea should be a good choice to exploit marine gas hydrates by combining solar and geothermal energy since this method has a great advantage either in terms of efficiency or cost.

Laboratory tests have been performed using a stirred cell where SI and SII gas hydrates have been formed under the presence of the kinetic inhibitor Poly Vinyl Caprolactam (PVCap) and INHIBEX. The latter is a mixture containing 50wt% PVCap 2k and 50wt% butyl glycol. The effect of PVCap is enhanced by the presence of butyl glycol; the latter acts as a synergist for the former. Dissociation temperatures were obtained and compared for hydrates formed 1) in presence of PVCap and 2) in presence of INHIBEX. The effect of INHIBEX concentration on the temperature of dissociation was also investigated. Systems containing INHIBEX dissociated at lower temperatures than the corresponding systems with only PVCap present. Furthermore, 3000 ppm INHIBEX mixtures were found to have higher dissociation temperatures than 1500 ppm INHIBEX mixtures.