This paper introduces the research advances on replacement of CH₄ in Natural Gas Hydrates (NGHs) by use of CO₂ and discusses the advantages and disadvantages of the method on the natural gas production from such hydrates. Firstly, the feasibility of replacement is proven from the points of view of kinetics and thermodynamics, and confirmed by experiments. Then, the latest progress in CH₄ replacement experiments with gaseous CO₂, liquid CO₂ and CO₂ emulsion are presented Moreover, the superiority of CO₂ emulsion for replacement of CH₄ is emphasized. The latest experiment progress on preparation of CO₂ emulsions are introduced. Finally, the advancements in simulation research on replacement is introduced, and the deficiencies of the simulations are pointed. The factors influencing on the replacement with different forms of CO₂ are analyzed and the optimum conditions for the replacement of CH₄ in hydrated with different forms of CO₂ is suggested.

The mechanical properties of methane hydrate are important to the stability of borehole and methane extraction from a methane hydrate reservoir. In this study, a series of triaxial compression tests were carried out on laboratory-formed methane hydrate-ice mixtures with various methane hydrate contents. Axial loading was conducted at an axial strain rate of 1.33%/min and a constant temperature of −10 °C. The results indicate that: (1) the deformation behavior is strongly affected by confining pressure and methane hydrate content; (2) the failure strength significantly increases with confining pressure when confining pressure is less than 10 MPa, and decreases with methane hydrate content; (3) the cohesion decreases with methane hydrate content, while the internal friction angle increases with methane hydrate content; (4) the strength of ice specimens are higher than that of methane hydrate-ice mixture specimens; Based on the experimental data, the relationship among failure strength, confining pressure and methane hydrate content was obtained, and a modified Mohr-Coulomb criterion considering the influence of methane hydrate content on shear strength was proposed.

The heat transfer analysis of hydrate-bearing sediment involved phase changes is one of the key requirements of gas hydrate exploitation techniques. In this paper, experiments were conducted to examine the heat transfer performance during hydrate formation and dissociation by a thermal method using a 5L volume reactor. This study simulated porous media by using glass beads of uniform size. Sixteen platinum resistance thermometers were placed in different position in the reactor to monitor the temperature differences of the hydrate in porous media. The influence of production temperature on the production time was also investigated. Experimental results show that there is a delay when hydrate decomposed in the radial direction and there are three stages in the dissociation period which is influenced by the rate of hydrate dissociation and the heat flow of the reactor. A significant temperature difference along the radial direction of the reactor was obtained when the hydrate dissociates and this phenomenon could be enhanced by raising the production temperature. In addition, hydrate dissociates homogeneously and the temperature difference is much smaller than the other conditions when the production temperature is around the 10 °C. With the increase of the production temperature, the maximum of ΔT_oi grows until the temperature reaches 40 °C. The period of ΔT_oi have a close relation with the total time of hydrate dissociation. Especially, the period of ΔT_oi with production temperature of 10 °C is twice as much as that at other temperatures. Under these experimental conditions, the heat is mainly transferred by conduction from the dissociated zone to the dissociating zone and the production temperature has little effect on the convection of the water in the porous media.

The porous microstructure of hydrates governs the mechanical strength of the hydrate-bearing sediment. To investigate the growth law and microstructure of hydrates in porous media, the growth process of tetrahydrofuran (THF) hydrate under different concentration of THF solution is directly observed using Magnetic Resonance Imaging (MRI). The images show that the THF hydrate grows as different models under different concentration of THF solution (19%, 11.4% and 5.7% by weight) at 1 °C. When the concentration is 19% (stoichiometric molar ratio of THF/H₂O = 1:17), the THF hydrate grows as cementing model. However, with the decreasing concentration of THF, the growth model transfers from cementing model to floating model. The results show that the growth of the THF hydrate was influenced by the dissolved quantity of THF in the water. The extension of the observed behavior to methane hydrate could have implications in understanding their role in seafloor and permafrost stability.

Creep behaviors of methane hydrate-bearing frozen specimens are important to predict the long-term stability of the hydrate-bearing layers in Arctic and permafrost regions. In this study, a series of creep tests were conducted, and the results indicated that: (1) higher deviator stress (external load) results in larger initial strain, axial strain, and strain rate at a specific elapsed time. Under low deviator stress levels, the axial strain is not large and does not get into the tertiary creep stage in comparison with that under high deviator stress, which can be even up to 35% and can cause failure; (2) both axial strain and strain rate of methane hydrate-bearing frozen specimens increase with the enhancement of deviator stress, the decrease of confining pressure, and the decrease of temperature; (3) the specimens will be damaged rather than in stable creep stage during creeping when the deviator stress exceeds the quasi-static strength of the specimens.

The ice generation is one of the challenges facing the methane hydrate depressurization, which, however, has not been fully addressed by existing numerical models for hydrate-bearing sediments (HBS). In this study, we develop a high-fidelity, fully coupled thermo-hydro-mechanical-chemical numerical model that incorporates the effect of ice. The model, developed using COMSOL, takes into account water–ice phase change, thermally induced cryogenic suction and constitutive relation in HBS. It is verified well against the temperature, pressure and cumulative gas production of Masuda’s experiment. The model is then employed to investigate multiphysical responses and gas/water production when ice generation is induced by setting a low outlet pressure. The results reveal that ice forms near the outlet boundary of the specimen center, leading to a reduction in intrinsic permeability and fluid velocity and an increase in the bulk modulus of ice-HBS. This enhanced bulk modulus results in higher porosity under axial load. Although the exothermic effect of ice generation promotes the hydrate dissociation, the effect on cumulative gas production is negligible after the ice melts. A negative correlation between ice saturation and water production rate is observed, indicating that a higher gas–water ratio can be achieved by adjusting the ice duration during hydrate production. The developed coupled model proves to be crucial for understanding the effect of ice on hydrate exploitation.