Heterogeneous nucleation of CO2 hydrate: A thermodynamics analysis considering effects of wall characteristics and solution activity

The massive emission of greenhouse gas CO2 has significant effects on global climate and environment, causing worldwide concern. It has been proposed to store CO2 in clathrate hydrates as a possible strategy for reducing atmospheric CO2 emission. Nevertheless, the CO2 hydrate formation rate is slow and its associated heterogeneous nucleation mechanisms are not well understood, which limit commercial applications of this technology. This study developed a thermodynamic model based on the change in availability function approach, considering effects of surface characteristics (including surface topography, roughness, curvature radius, and wettability), and CO2 dissolution on the solution's activity. The critical nucleation radius and energy barrier of CO2 hydrate nucleation are determined. Effects of pressure, temperature, wall characteristics and solution activity on the nucleation radius of CO2 hydrate are discussed. The results of this paper contribute to advancing carbon capture and storage technology based on hydrate methods.