title: Origin of Self-preservation Effect for Hydrate Decomposition: Coupling of Mass and Heat Transfer Resistances.
abstract: Gas hydrates could show an unexpected high stability at conditions out of thermodynamic equilibrium, which is called the self-preservation effect. The mechanism of the effect for methane hydrates is here investigated via molecular dynamics simulations, in which an NVT/E method is introduced to represent different levels of heat transfer resistance. Our simulations suggest a coupling between the mass transfer resistance and heat transfer resistance as the driving mechanism for self-preservation effect. We found that the hydrate is initially melted from the interface, and then a solid-like water layer with temperature-dependent structures is formed next to the hydrate interface that exhibits fractal feature, followed by an increase of mass transfer resistance for the diffusion of methane from hydrate region. Furthermore, our results indicate that heat transfer resistance is a more fundamental factor, since it facilitates the formation of the solid-like layer and hence inhibits the further dissociation of the hydrates. The self-preservation effect is found to be enhanced with the increase of pressure and particularly the decrease of temperature. Kinetic equations based on heat balance calculations is also developed to describe the self-preservation effect, which reproduces our simulation results well and provides an association between microscopic and macroscopic properties.
authors.affiliation: Department of Chemistry, School of Science, Beijing Technology and Business University, Beijing, 100048, P.R. China.|State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, P.R. China.
authors.forename: Dongsheng
authors.initials: D
authors.lastname: Bai
authors.affiliation: Department of Chemistry, School of Science, Beijing Technology and Business University, Beijing, 100048, P.R. China.
authors.forename: Diwei
authors.initials: D
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, P.R. China.
authors.forename: Xianren
authors.initials: X
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Heavy Oil Processing, School of Chemical Engineering, China University of Petroleum, Beijing, 102249, P.R. China.
authors.forename: Guangjin
authors.initials: G
authors.lastname: Chen