Growth rate of CO2 and CH4 hydrates by means of molecular dynamics simulations

Abstract

CO2 and CH4 hydrates are of great importance both from an energetic and from an environmental point of view. It is therefore highly relevant to quantify and understand the rate with which they grow. We use molecular dynamics simulations to shed light on the growth rate of these hydrates. We put the solid hydrate phase in contact with a guest aqueous solution in equilibrium with the pure guest phase and study the growth of both hydrates at 400 bars with temperature. We compare our results with previous calculations of the ice growth rate. We find a growth rate maximum as a function of the supercooling in all cases. The incorporation of guest molecules into the solid structure strongly decelerates hydrate growth. Consistently, ice grows faster than either hydrate and the CO2 hydrate grows faster than the CH4 one because of the higher solubility of CO2. We also quantify the molecular motion required to build the solids under study and find that the distance traveled by liquid molecules exceeds by orders of magnitude that advanced by any solid. Less molecular motion is needed in order for ice to grow as compared to the hydrates. Moreover, when temperature increases, more motion is needed for solid growth. Finally, we find a good agreement between our growth rate calculations and experiments of hydrate growth along the guest–solution interface. However, more work is needed to reconcile experiments of hydrate growth toward the solution among each other and with simulations.