The morphology of liquid CO2 hydrate films at different temperatures under saturation pressure

CO2 hydrate film formed on the surface of water droplets in liquid CO2 was studied via digital microscope system and in situ Raman spectrometer. Temperature significantly affects the initial morphology and lateral growth rate of hydrate film. In the temperature range of 273.15-279.15 K under corresponding saturation pressure of liquid CO2, the growth and development process is primarily separated into three stages, that is, rapid lateral growth, rapid thickening, and slow development. However, in the temperature range of 280.15-282.15 K, the growth and evolution of hydrated film is dominated by rapid lateral growth and slow development processes, while the rapid thickening disappears on our experimental scale, caused by the decrease in the driving force. Each of these two temperature ranges has unique characteristics and interesting discoveries during the hydrate film formation and development. For hydrate film formed at 283.15 K, the formation of hydrate is very difficult. It needs to nucleate inside the droplet with the assistance of the hydrate crystal seeds remaining in the water droplet after decomposition, so that the small hydrate crystals can grow in the water phase, and as the crystals get larger, they will eventually emerge on the droplet's surface and produce a complete hydrate film. Combining the experimental phenomena during the growth and development of hydrate films at various temperatures, the further growth of the hydrate phase during the generation process mainly depends on the mass transfer process of water molecules through the hydrate film. This work provides valuable information on the mechanism of nucleation, growth and decomposition of liquid CO2 hydrate crystals, which is of great significance for applications in seafloor CO2 gas sequestration.