Molecular guest exchange and subsequent structural transformation in CH4 – CO2 replacement occurring in sH hydrates as revealed by 13C NMR spectroscopy and molecular dynamic simulations

[Display omitted] •The mechanism of the structural transformation during replacement is investigated.•A higher CO2 enclathration ratio causes the structural transition from sH to sI.•CO2 molecules preferentially occupy sI large cages and sH medium cages.•A lower CO2 enclathration ratio results in a lower extent of replacement. This study adopted experimental and computational approaches to investigate CH4 – CO2 replacement in the structure H (sH) CH4 + methylcyclopentane (MCP) hydrate for its dual functions of CH4 recovery and CO2 sequestration. Hydrate phase equilibria, 13C NMR spectra, and molecular dynamics (MD) simulations of CH4 + MCP – CO2 replacement were examined and compared with those of CH4 + neohexane (NH) – CO2 replacement to elucidate the molecular guest exchange behaviors in both systems. The structure I (sI) hydrates were thermodynamically favored in CO2-rich gas mixtures (CH4 + CO2 + MCP systems), and a structural transformation from sH to sI occurred when CO2 composition in the feed gas was higher than 20 %. The 13C NMR spectra indicated that the CO2 molecules preferred to occupy the large (51262) cages of sI and the medium (435663) cages of sH compared to the small (512) cages of both sI and sH during replacement. Following CO2 injection into the sH CH4 + MCP hydrate, the initial sH hydrate transformed to the sI hydrate with CH4 recovery of approximately 78 %. The MD simulations also demonstrated that structural transformation in the CH4 + MCP – CO2 replacement would occur at the lower CO2 enclathration ratio compared to the CH4 + NH – CO2 replacement, thereby leading to a lower CO2 concentration in the newly formed sI hydrate. This is the first study to provide both experimental and computational evidence of guest-dependent structural transformation in sH CH4 + liquid hydrocarbons – CO2 replacement.