Analysis of Influencing Factors and Kinetic Characteristics of Spherical Methane Hydrate Decomposition

Abstract

Herein, several molecular systems are simulated by molecular dynamics to study the decomposition process and fluctuation-dissipation characteristics of spherical methane hydrates under different conditions. The spherical radius and the movement of the hydrate-liquid water interface during decomposition are measured. Different fitted formulas of the variation of methane numbers are obtained from the decomposition of spherical and bulk methane hydrates. Fluctuation-dissipation characteristics for spherical methane hydrates with different radii are analyzed, which show that increasing the scale of hydrates can increase the relaxation time and slow down the fluctuation process. The variations of the hydrogen bond and hydrogen-bond lifetime are calculated. For hydrate phase water, the peak of the hydrogen-bond lifetime lies between 8 and 10 ps. After complete decomposition, the hydrogen-bond lifetime mainly distributes in 0 and 2 ps and the peak disappears. The effects of temperature, cage occupancy, liquid phase environment, and spherical hydrate scale are explored. The decomposition activation energy for the spherical hydrate with a radius of 20 Å is calculated to be 52.23 kJ/mol. It can speed up the decomposition rate as well as the diffusion of methane and water molecules with a lower cage occupancy. For the effect of the liquid phase environment, it is found that the number of liquid water rarely affects the decomposition. However, when the Na+ and Cl- concentrations change from 0 to 10%, the decomposition time reduces from ∼511 to ∼369 ps, which indicates that there is an obviously positive impact on decomposition.