Large-Scale Nonequilibrium Molecular Studies of Thermal Hydrate Dissociation.

The energy content of methane hydrate reservoirs (MHRs) is at least twice that of conventional fossil fuels. So, there is considerable interest in their commercial development by heating, among other dissociation mechanisms. However, a few researchers have highlighted the potentially uncontrollable release of methane from MHRs, which could occur because of global warming. Therefore, it is crucial to understand the kinetics of thermal hydrate dissociation to safely develop these resources and prevent the release of this greenhouse gas into the environment. Although there have been several molecular studies of thermal dissociation, most of these use small simulation domains that cannot capture the transient nature of the process. To address this limitation, we performed coarse-grained molecular dynamics (CGMD) simulations on a significantly larger domain with a hundred times more hydrate unit cells than those used in previous studies. We monitored the kinetics of dissociation using an image-processing algorithm and observed the dynamics of the process while maintaining a thermal gradient at the dissociation front. For the first time, we report the formation of an unstable secondary dissociation path that triggers gas bubbles within the solid hydrate. The kinetics of thermal dissociation appears to occur in three stages. In the first stage, the energy of the system increases until it exceeds the activation energy, and dissociation is initiated. Consistent dissociation occurs in the second stage, whereas the third stage involves the dissociation of the remaining hydrates across a nonplanar and heterogeneous interface.