Kinetic study on the effect of ice nucleation and generation on methane hydrate dissociation below the quadruple point

Abstract

Natural gas hydrates (NGHs) have captured worldwide attention because of its huge resources and high energy density. Deep depressurization by dropping the pressure below the quadruple point is recognized as a promising exploitation method. However, the impact of ice formation on NGHs dissociation within depressurization is still controversial. Thus, we examine the dissociative behavior of NGHs at low temperature below the quadruple point using a high-pressure reactor. It primarily focuses on how ice formation affects heat and mass transfer, as well as the kinetics of hydrate dissociation. The results indicate that during the hydrate dissociation process, liquid water initially transforms into metastable supercooled water, which then transitions to solid ice under external disturbance. Ice nucleation predominantly occurs in two locations: within the free water phase and on the surface of hydrate particles. A double-edged effect of ice on NGHs dissociation is observed: the latent heat released by ice nucleation and generation could accelerate the hydrate breakdown (positive effect), while the decrease in permeability along with the self-preservation effect from ice formation tends to inhibit the NGHs dissolution (negative effect). In addition, a higher pressure drawdown rate can accelerate both ice nucleation and formation, which in turn shortens the freezing induction time. The increase of water saturation (S_A) and the decrease of hydrate saturation (S_H) can significantly reduce the mining time and strengthen both the hydrate dissociation rate (Q_H) and gas production rate (Q_P). Therefore, hydrate sediments with higher S_A or lower S_H are more conductive to gas recovery of low-temperature NGHs deposits in permafrost regions.