Hydrate dissociation is often accompanied by the formation of nanobubbles. Knowledge of the effects of nanobubbles on hydrate dissociation is essential for understanding the dynamic behavior of the hydrate phase change and improving the gas production efficiency. Here, molecular dynamics simulations were performed to study the methane hydrate dissociation kinetics with and without a pre-existing methane nanobubble. The results show that the hydrate cluster in the liquid phase dissociates layer-by-layer. This process is shown to be independent of the temperature and nanobubble presence at the simulation conditions. Hydrate dissociation does not always lead to nanobubble formation because the supersaturated methane solution can be stable for a long time. A steep methane concentration gradient was observed between the hydrate cluster surface and the methane nanobubble, which can enhance the directional migration of methane and effectively minimize the methane concentration in the liquid phase, thereby increasing the driving force for the hydrate dissociation. Our findings indicate that the presence of a nanobubble near the hydrate surface does not decrease the activation energy of hydrate dissociation, but it can increase the intrinsic decomposition rate. The average hydrate dissociation rate is linearly correlated with the mass flow rate towards the nanobubble. The mass flow rate is determined by the nanobubble size and hydrate-nanobubble distance. Our findings contribute to the fundamental understanding of the dissociation mechanism of gas hydrates in the liquid phase, which is crucial for the design and optimization of efficient gas hydrate production techniques.@en

An understanding of the dynamic behavior of subtle hydrate dissociation in the liquid water phase is fundamental for gas production from marine hydrate reservoirs. Molecular dynamics simulations are performed in this study to investigate the dissociation kinetics of pure propane and binary propane + methane sII hydrates in a liquid water environment. The results show that faster hydrate dissociation rates are observed at higher initial temperatures. The hydrate phase dissociates from the cluster surface to the inside in a layer-by-layer manner under the simulation temperature conditions, which is similar to the behavior of sI hydrates and is independent of the hydrate crystal type. Compared to the binary sII hydrate, the pure sII hydrate dissociates more easily under the same initial temperature conditions, which can be attributed to the stabilizing effect of guest molecules in the hydrate cages. The empty cages collapse in one step, in contrast to the two-step pathway induced by the guest-host interaction. In addition, a hydrocarbon phase forms in the binary hydrate dissociation system instead of nanobubbles. These results can provide molecular-level insights into the dynamic mechanism of hydrate dissociation and theoretical guidance for gas recovery by thermal injection from marine hydrate reservoirs. @en

Knowledge on the kinetics of gas hydrate dissociation in clay pores at static and dynamic fluid conditions is a fundamental scientific issue for improving gas production efficiency from hydrate deposits using thermal stimulation and depressurization respectively. Here, molecular dynamics simulations were used to investigate poly- and mono-crystalline methane hydrates in Na-montmorillonite clay nanopores. Simulation results show that hydrate dissociation is highly sensitive to temperature and pressure gradients, but their effects differ. Temperature changes increase thermal instability of water and gas molecules, leading to layer-by-layer dissociation from the outer surface. Under flow conditions, laminar flow predominates in nano-pores, and non-Darcy flow occurs due to clay-fluid interactions. Viscous flow disrupts hydrogen bonding at the hydrate surface, enhancing kinetic instability of water. Grain boundaries of polycrystalline hydrates are less stable compared to bulk phases and preferentially decompose, forming new dissociation fronts. This accelerates dissociation compared to monocrystalline hydrates. Fracture occurs at the grain boundaries of polycrystalline hydrate in the fluid, resulting in separate hydrate crystal grains. This fracture process further accelerates hydrate dissociation. In flow systems, methane nanobubbles form in fluid and readily transport with fluid flow. Unlike surface nanobubbles at static conditions, these liquid nanobubbles exhibit mobility. The findings of this study can contribute to a better understanding of the complex phase transition behavior of hydrate in confined environment, and provide theoretical support for improving production control technology.@en

The trial production of natural gas hydrate reservoirs remains poor. Reasonable reservoir reconstruction, which can improve formation permeability, is an important approach to increasing the efficiency and enhancing production. In this work, water jet slotting is proposed to reconstruct an natural gas hydrate reservoir near a wellbore. The spatial slots formed by water jet slotting not only directly constitute high-permeability channels, but also generate disturbances to the surrounding in-situ sediment. Water jet slotting disturbances to nearby sediment was investigated using a three dimensional flow-structure coupling model to evaluate the proposed reconstruction method. The reservoir at the SH2 site in the Shenhu area of the South China Sea was used as the reference. A horizontal slotting arrangement along the vertical well was adopted. The results demonstrate that water jet slotting can change the primary stress state of the sediment around the wellbore, and generate a dominant stress relaxation zone and small stress concentration zone. Within the stress relaxation zone, the in-situ compressive stress was remarkably reduced or even transformed into tensile stress, accompanied by sediment displacement and volumetric expansion strain. This is conducive to loosening the sediment around the wellbore and improving the permeability characteristics. In addition, the influence of the water jet slotting parameters including slot radius, spacing, and number on disturbances to the nearby sediment was studied. Reservoir responses to water jet slotting under balanced and unbalanced bottom-hole pressures were compared and analyzed. This study provides a reference for natural gas hydrate reservoir reconstruction using water jet slotting.@en

Methane hydrate dissociation kinetics can be inhibited in NaCl solutions; however, this effect is reversed by promoting bubble formation that enhances dissociation. The negative and positive effects of inorganic salt injection on gas production from hydrate-bearing sediments are still controversial. Here, molecular dynamics simulations were performed to investigate the characteristics of NaCl solution invasion into hydrate-occupied nanopores and the effects on the confined hydrate dissociation kinetics. Two initial configurations comprising liquid and silica pore phases were studied with a low or high NaCl concentration, respectively. The results show that, under the simulation conditions, salt invasion decelerated hydrate dissociation within the silica pore as NaCl invasion into the pore is stepwise. Initially, few ions can diffuse into the pore phase, and gas nanobubbles form on the solid surface mainly via confinement and surface effects, independent of NaCl solution invasion. Subsequently, gradual salt diffusion immersed the residual hydrate in the salt solution and hindered hydrate decomposition until the dissociation finished. More ions could diffuse into the pore phase at the high NaCl concentrations with a low diffusion efficiency, leading to surface nanobubble growth toward the residual hydrate and somewhat accelerated hydrate dissociation. This severely hinders the escape of released methane from the pore. This study yields molecular-level insight into the origin of the negative effect of salt invasion on hydrate dissociation, which should be avoided during gas production from hydrate reservoirs with low permeabilities via salt injection combined with thermal stimulation. @en

Continuous Fractional Component Monte Carlo (CFCMC) and molecular dynamics (MD) simulations are performed to calculate the solubilities and self-diffusion coefficients of four light n-alkanes (methane, ethane, propane, and n-butane) in aqueous NaCl solutions as well as the thermodynamic properties of their corresponding hydrate crystals. Correction factors kij to the Lorentz-Berthelot combining rules for alkane groups (CH3) and water are optimized (kij = 1.04) by fitting excess chemical potentials to experimental data at 1 bar and 298.15 K. Using these values of kij, we calculate the solubilities of the four alkanes in aqueous NaCl solutions with different molalities (0-6) mol/kg at different temperatures (278.15-308.15) K and pressures (1, 100, 200, 300) bar. The diffusion coefficients of the four alkanes in NaCl solutions (0-6) mol/kg are calculated at different temperatures (278.15-308.15) K and 1 bar and corrected for the finite-size effects. The lattice parameters of the corresponding hydrates with different guest molecules are computed using MD simulations at different temperatures (150-290) K and pressures (5-700) MPa. Isothermal compressibilities at 287.15 K and thermal expansion coefficients at 14.5 MPa for the corresponding hydrates are calculated. We present an extensive collection of thermodynamic data related to gas hydrates that contribute to a fundamental understanding of natural gas hydrate science.@en