Molecular Dynamics Simulations of Methane Hydrate Pre-nucleation Phenomena and the Effect of PVCap Kinetic Inhibitor

摘要

MD simulations were employed to investigate a number of different systems of relevance for methane hydrate formation, dissociation and inhibition. Regions of stability for methane hydrate have been investigated using a model system consisting of a slab of hydrate embedded in liquid water. Water/methane interface structuring and possible precursors to hydrate formation have been investigated using a model system of water and methane at different densities. In yet another system we have investigated the impact of Dodecamers (twelve-unit molecules) of poly (vinyl caprolactam) or PVCap on structuring of water/methane interfaces. PVCap is well known for its performance as hydrate kinetic inhibitor. Intermolecular interactions were treated by a combination of Coulomb and Lennard-Jones potentials. Temperature was controlled by a simple velocity scaling. Several of the hydrate-containing systems showed a tendency to melt when in contact with methane-saturated water even at temperatures well below the hydrate stability region. We have attributed this behavior to the fact that hydrate volume available in a MD experiment is small and lacks the stabilizing presence of bulk. Systems containing liquid water and methane showed certain signs of hydrate nucleation. The PVCap behavior was shown to be very dependent on its concentration in water. At low concentrations, PVCap tended to prefer the water-methane interface and not to interact with each other, similarly to another kinetic inhibitor, PVP. When the liquid PVCap content was high, it evidently modified the interfacial tension of water-methane surface, converting the initially disperesed methane phase into separated bubbles. The PVCap molecules then built a system-wide network that partially covered the surface of methane bubbles.