Dynamic morphology of clathrate hydrates in porous media

Natural gas hydrates represent a significant and widely distributed potential energy source globally. Furthermore, hydrates are also considered a possible carbon capture and storage method in the permafrost and deep ocean sea areas. Hydrate morphology is critical in determining the sediments' flow properties and production/storage efficiency. However, the dynamic morphology remains unclear, especially in the microscale. This study was performed by MH21-S and funded by the Ministry of Economy, Trade and Industry, and we used our self-invented micromodels (micron level) for hydrate formation in an air bath of 1 °C for several months. Meanwhile, the state-of-the-art high-resolution microscope was used to detect the dynamic morphology of hydrate formation and dissociation. The result showed that the hydrate growth mechanism could be divided into four stages due to different driving forces: hydrate fingering formation, Ostwald ripening phenomenon, hydrate contraction, and heterogeneous hydrate dissociation processes. In the first stage, the hydrate fingering formation process consistently occurs from the inlet to the outlet area, and the fingering process stops after several days. In the second stage, the Ostwald ripening phenomenon was detected in the microscale for the first time. Smaller hydrate particles first dissolved and then redeposited onto larger hydrate particles, which is a spontaneous process. In the third stage, the surface area of hydrates tends to reduce to reach a more stable phase, resulting in the hydrate contraction. Finally, manual temperature increases induce heterogeneous hydrate dissociation. Our study aims to enhance the understanding of hydrate behaviors in sediments over an extended period.