Mechanistic insights into pore water conversion to gas hydrates in clay minerals

Abstract

The conversion of pore water to gas hydrates is an important prerequisite for natural gas hydrates (NGHs) accumulation and hydrate-based CO2 sequestration. However, the mechanism of water-to-hydrate conversion in clays, which are prevalent in hydrate reservoirs or marine sediments serving as potential hosts for CO2 hydrates, still remains poorly understood, impeding further advancements in exploiting NGHs and developing CO2 sequestration strategies. In this paper, the characteristics of pore water conversion to hydrates in montmorillonite and kaolin were comprehensively examined through quantitative measurements and NMR analysis, and compared with those in silt and coarse sand. It revealed that the water-to-hydrate conversion was more restricted in clays than in sands. Especially in montmorillonite, since almost all pore water was detected as bound water, the final water conversion was extremely low and sensitive to the subcooling degree. Additionally, as the initial water content increased from 15 wt% to 35 wt%, the final water conversion in kaolin, silt, and coarse sand decreased exponentially due to intensified kinetic limitation, whereas that in montmorillonite initially rose and then fell, attaining the maximum at a threshold of 20 wt%. It is found that the competition between thermodynamic and kinetic limitations controls water-to-hydrate conversion in clays. Specifically, in kaolin, silt and coarse sand, the main controlling factor of water-to-hydrate conversion is the kinetic limitation, as their unconverted equilibrium water is negligible. However, in montmorillonite, the thermodynamic limitation dominates at low water contents, transitioning to kinetic limitation at high water contents. This study provides direct evidence and mechanistic insights into how clays affect water-to-hydrate conversion in porous media, which has significant implications for the geological accumulation of NGHs and the site selection for hydrate-based CO2 sequestration.