Molecular scale modeling approach to evaluate stability and dissociation of methane and carbon dioxide hydrates

A comprehensive knowledge and precise estimation of the dynamic, structural, and thermodynamic characteristics of hydrates are needed to assess the stability of gas hydrates. Thermodynamic model and experimental studies can be utilized to compute the physical and dynamic properties of hydrate structures. The use of molecular dynamic (MD) simulation is a well-established approach in gas hydrate studies at the atomic level where the properties of interest are obtained from the numerical solution of Newtonian equations. The present work uses MD simulations by employing the constant temperature-constant pressure (NPT), constant temperature-constant volume (NVT) conditions, and the consistent valence force field (CVFF) to monitor the stability and decomposition of methane and carbon dioxide gas hydrates with different compositions. The effects of temperature and composition on the hydrate stability are investigated. In this study, we also compute the radial distribution function, mean square displacement, diffusion coefficient, lattice parameter, potential energy, dissociation enthalpy as well as the density of methane and carbon dioxide under various thermodynamic and process conditions. The formation of methane and carbon dioxide bubbles is studied to investigate bubble evolution during hydrate dissociation. The sizes of methane and carbon dioxide bubbles are not the same due to different solubility conditions of methane and carbon dioxide in liquid water. In addition, the influences of pressure and temperature on the lattice parameter and density of clathrate hydrates are discussed. The obtained results are consistent with previous theoretical and experimental findings, implying that the methodology followed in this work is reliable. The most stable arrangement of methane and carbon dioxide molecules in the gas hydrate is found. The insights/ findings of this study might be useful to further understand detailed transport phenomena (e.g., molecular interactions, gas production rate, carbon dioxide replacement, and carbon dioxide capture) involved in the process of carbon dioxide injection into gas hydrate reservoirs. (C) 2019 Elsevier B.V. All rights reserved.