The characteristics of the hydrate-bearing layer are important parameters for gas hydrate exploration and exploitation, which can be provided by laboratory analysis. We have carried out a systematic analysis of modern instruments, including the laser grain size analyzer, X-ray computed tomography, scanning electron microscopy, X-ray diffraction (XRD), Raman spectroscopy, gas chromatography, and isotope mass spectrometry, on the hydrate-bearing sediment samples recovered from the Shenhu area in the South China Sea in 2016. We focused on the structure, hydration number, and gas composition of the gas hydrate samples. We also evaluated the effects of sediments on the occurrence and distribution of gas hydrate. Our results showed that the sediments are much finer than those recovered from the Shenhu area in 2007. Some samples are found to contain calcareous microfossils and foraminifera, which are beneficial for dispersed gas hydrate formation. Whereas the only visible hydrate sample (FC4) has not found any bioclast in the sediments. Based on the Raman data and the XRD analysis, the gas hydrates demonstrate typical structure I (sI) hydrates, with cage occupancies of methane molecules higher than 99.3% in large cages and 81.5%–91.4% in small cages, respectively. The crystal lattice parameter is 11.89 Å with the hydration number being approximately 6.0. Methane is obviously the dominant component, ranging from 97.6% to 99.95% in these samples. Comprehensive study of carbon and hydrogen isotopes suggests that the hydrate-bound gases are from biogenic and thermogenic gases in the study area.

Geophysical detection techniques are important methods in marine gas hydrate exploration and monitoring, because the small-scale distribution of hydrates has a large impact on the wave velocity. The acoustic response characteristics of hydrate micro-distributions have strong significance for monitoring the hydrate dissociation process. In this paper, experiments simulating the hydrate dissociation process were carried out in a self-developed experimental device combining X-ray computed tomography (X-CT) scanning and ultrasonic detection, which allowed the acoustic wave characteristics and X-CT scanning results to be simultaneously obtained during the hydrate dissociation process. This study found that the hydrate dissociation stage is divided into three stages. The hydrate begins to dissociate at spots where it comes into touch with sand particles early in the dissociation process. The main factor affecting the acoustic wave velocity of hydrates in this stage is changes in the microscopic distribution of hydrate. In the middle stage, a large amount of hydrate decomposes, and the main factor affecting the acoustic wave velocity of hydrate in this stage is the change in hydrate content. In the later stage of hydrate dissociation, the hydrate distribution pattern consists mainly of the pore-filling type, and the hydrate micro-distribution at this stage is the main factor affecting the acoustic wave velocity. This study will be of great significance for understanding the microscopic control mechanism of hydrate reservoir geophysical exploration.

Mechanical properties of hydrate-bearing sediments (HBS) are crucial for evaluating drilling- and production-induced geo-hazards. However, investigations on mechanical behaviors of clayey-silt samples containing hydrate are insufficient due to low efficiency in preparing reconstituted hydrate-bearing samples. Herein, we carried out a series of triaxial shear tests to analyze the deformation behaviors of reconstituted clayey-silt samples containing tetrahydrofuran (THF) hydrate. The sediments were taken from the Shenhu Area, northern South China Sea. The failure mechanisms during shearing are discussed based on micro-to-macro analyses. The results imply that the stress-strain curves show obvious strain-hardening under triaxial shearing, which can be divided into elastic deformation stage, transitional stage, and plastic deformation stage. Besides, the results reveal that cohesion strengthens from 0.09 MPa to 1.28 MPa when hydrate saturation increases from 15% to 60%. Moreover, calculation models are proposed to evaluate failure strengths and Young’s modulus. Establishing empirical formula based on experimental data can quickly determine the strength parameters with knowing the hydrate saturation and stress state of clayey-silt sediments containing hydrate. It is urgent in field operations and numerical simulation to use reliable empirical models.

Molecular dynamics (MD) simulations were performed to determine the three-phase coexistence line of sI methane hydrates. The MD simulations were carried out at four different pressures (4, 10, 40, and 100 MPa) by using the direct phase coexistence method. In current simulations, water was described by either TIP4P/Ice or “optimal” point charge (OPC) models and methane was described as a simple Lennard-Jones interaction site. Lorentz–Berthelot (LB) combining rules were used to calculate the parameters of the cross interactions. For the OPC model, positive deviations from the energetic LB rule were also considered based on the solubility of methane in water. For the TIP4P/Ice water model, the obtained three phase coexistence temperatures showed good agreement with experiment data at higher pressures, which is consistent with previous predictions. For the OPC water model, simulations using the classic and the modified LB parameters both showed negative deviations to the experimental values. Our results also indicated that the deviation of the T₃ prediction by the OPC model was not closely correlated with the predicted melting point of ice. At 4 MPa, the modified OPC model showed a better prediction of hydrate equilibrium temperature, even better than the prediction by TIP4P/Ice. Considering the relatively higher accuracy in biomolecular MD of the OPC model, it is suggested that this model may have a better performance in hydrate MD simulations of biomolecule-based additives.

CH₄/CO₂ replacement is of great significance for the exploitation of natural gas hydrate resources and CO₂ storage. The feasibility of this method relies on our understanding of the CH₄/CO₂ replacement efficiency and mechanism. In this study, CH₄/CO₂ replacement experiments were carried out to study the distribution characteristics of CH₄ and CO₂ in hydrate-bearing sediments during and after replacement. Similar to previously reported data, our experiments also implied that the CH₄/CO₂ replacement process could be divided into two stages: fast reaction and slow reaction, representing CH₄/CO₂ replacement in the hydrate-gas interface and bidirectional CH₄/CO₂ diffusion caused replacement, respectively. After replacement, the CO₂ content gradually decreased, and the methane content gradually increased with the increase of sediment depth. Higher replacement percentage can be achieved with higher replacement temperature and lower initial saturation of methane hydrate. Based on the calculation of CO₂ consumption amounts, it was found that the replacement mainly took place in the fast reaction stage while the formation of CO₂ hydrate by gaseous CO₂ and water almost runs through the whole experimental process. Thus, the pore scale CH₄/CO₂ replacement process in sediments can be summarized in the following steps: CO₂ injection, CO₂ diffusing into sedimentary layer, occurrence of CH₄/CO₂ replacement and CO₂ hydrate formation, wrapping of methane hydrate by mixed CH₄-CO₂ hydrate, continuous CO₂ hydrate formation, and almost stagnant CH₄/CO₂ replacement.

As a future clean energy resource, the exploration and exploitation of natural gas hydrate are favorable for solving the energy crisis and improving environmental pollution. Detecting the spatial distribution of natural gas hydrate in the reservoir is of great importance in natural gas hydrate exploration and exploitation. Fracture-filling hydrate, one of the most common types of gas hydrate, usually appears as a massive or layered accumulation below the seafloor. This paper aims to detect the spatial distribution variation of fracture-filling hydrate in sediments using the electrical property in the laboratory. Massive hydrate and layered hydrate are formed in the electrical resistivity tomography device with a cylindrical array. Based on the electrical resistivity tomography data during the hydrate formation process, the three-dimensional resistivity images of the massive hydrate and layered hydrate are established by using finite element forward, Gauss–Newton inversion, and inverse distance weighted interpolation. Massive hydrate is easier to identify than layered hydrate because of the big difference between the massive hydrate area and surrounding sediments. The diffusion of salt ions in sediments makes the boundary of massive hydrate and layered hydrate change with hydrate formation. The average resistivity values of massive hydrate (50 $\mathsf{\Omega }\cdot \mathrm{m}$) and layered hydrate (1.4 $\mathsf{\Omega }\cdot \mathrm{m}$) differ by an order of magnitude due to the difference in the morphology of the fracture. Compared with the theoretical resistivity, it is found that the resistivity change of layered hydrate is in accordance with the change tendency of the theoretical value. The formation characteristic of massive hydrate is mainly affected by the pore water distribution and pore microstructure of hydrate. The hydrate formation does not necessarily cause the increase in resistivity, but the increase of resistivity must be due to the formation of hydrate. The decrease of resistivity in fine-grains is not obvious due to the cation adsorption of clay particles. These results provide a feasible approach to characterizing the resistivity and growth characteristics of fracture-filling hydrate reservoirs and provide support for the in-situ visual detection of fracture-filling hydrate.