In this study, a nano‐focus X‐ray computed tomography (X‐CT) is used to observe the formation of methane hydrate in sands on pore scale and to quantify hydrate saturation, pore structure parameters, and permeability of hydrate‐bearing sands. A new analytical technique is developed to improve the identification of water‐hydrate boundary. Three hydrate accumulation habits (i.e., floating, contacting, and cementing) in pore spaces are observed. When there is no methane bubble, hydrate distribution evolves from floating to contacting and then to cementing as hydrate saturation increases. In contrast, only contacting and cementing distribution patterns appear in the pores with methane bubbles. Based on the surface extraction and defect detection from 3‐D images, both the gas/water/hydrate distributions and the pore structure characteristics are investigated. The results show that the porosity, the maximal pore volume, and maximal diameter decrease as hydrates accumulate in the pores. However, the maximal pore surface, the total pore number, and the large pores (>100 voxels) number increase gradually until the hydrate saturation reaches 35%, when they turn to decrease rapidly. The pore structure parameters show detailed changes of hydrate and water on pore scale. The incompressible Navier‐Stokes equations are used to calculate absolute permeability of hydrate‐bearing sands based on X‐ray computed tomography digital images. It indicates that the microdistribution of the hydrate has a significant effect on the permeability calculation. The fluid streamlines obtained through simulation are used to track the water transport paths.

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.

Characterizing the electrical property of hydrate-bearing sediments is essential for hydrate reservoir identification and saturation evaluation. As the major contributor to electrical conductivity, pore water is a key factor in characterizing the electrical properties of hydrate-bearing sediments. The objective of this study is to clarify the effect of hydrates on pore water and the relationship between pore water characteristics and the saturation exponent of Archie’s law in hydrate-bearing sediments. A combination of X-ray computed tomography and resistivity measurement technology is used to derive the three-dimensional spatial structure and resistivity of hydrate-bearing sediments simultaneously, which is helpful to characterize pore water and investigate the saturation exponent of Archie’s law at the micro-scale. The results show that the resistivity of hydrate-bearing sediments is controlled by changes in pore water distribution and connectivity caused by hydrate formation. With the increase of hydrate saturation, pore water connectivity decreases, but the average coordination number and tortuosity increase due to much smaller and more tortuous throats of pore water divided by hydrate particles. It is also found that the saturation exponent of Archie’s law is controlled by the distribution and connectivity of pore water. As the parameters of connected pore water (e.g., porosity, water saturation) decrease, the saturation exponent decreases. At a low hydrate-saturation stage, the saturation exponent of Archie’s law changes obviously due to the complicated pore structure of hydrate-bearing sediments. A new logarithmic relationship between the saturation exponent of Archie’s law and the tortuosity of pore water is proposed which helps to calculate field hydrate saturation using resistivity logging data.

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.