Salinity‐buffered methane hydrate formation and dissociation in gas‐rich systems

Methane hydrate formation and dissociation are buffered by salinity in a closed system. During hydrate formation, salt excluded from hydrate increases salinity, drives the system to three‐phase (gas, water, and hydrate phases) equilibrium, and limits further hydrate formation and dissociation. We developed a zero‐dimensional local thermodynamic equilibrium‐based model to explain this concept. We demonstrated this concept by forming and melting methane hydrate from a partially brine‐saturated sand sample in a controlled laboratory experiment by holding pressure constant (6.94 MPa) and changing temperature stepwise. The modeled methane gas consumptions and hydrate saturations agreed well with the experimental measurements after hydrate nucleation. Hydrate dissociation occurred synchronously with temperature increase. The exception to this behavior is that substantial subcooling (6.4°C in this study) was observed for hydrate nucleation. X‐ray computed tomography scanning images showed that core‐scale hydrate distribution was heterogeneous. This implied core‐scale water and salt transport induced by hydrate formation. Bulk resistivity increased sharply with initial hydrate formation and then decreased as the hydrate ripened. This study reproduced the salinity‐buffered hydrate behavior interpreted for natural gas‐rich hydrate systems by allowing methane gas to freely enter/leave the sample in response to volume changes associated with hydrate formation and dissociation. It provides insights into observations made at the core scale and log scale of salinity elevation to three‐phase equilibrium in natural hydrate systems.