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[Display omitted] • An approach of warm brine injection to promote CH 4 /CO 2 replacement is proposed. • Warm brine injection provides a 2.0 times enhancement of the cumulative gas yield. • A potential risk of hydrate reformation is alleviated by increasing salinity. • Gas production is insensitive to injected heat as the significant heat loss. • Brine injection scheme should be optimized based on energy harvest and CO 2 storage. CH 4 /CO 2 replacement for natural gas hydrates (NGHs) exploitation is a promising method for CO 2 geological sequestration and energy recovery simultaneously. However, the puzzles of low replacement efficiency and slow reaction rate caused by the mass transfer obstacle of gas exchange are fatal bottlenecks for field application of gas replacement method. Therefore, we propose a method that uses warm brine injection during CH 4 /CO 2 replacement process to break the barrier of CO 2 diffusion and enhance CH 4 recovery as well as CO 2 storage. Benefiting from the synergistic influence of salt effect and thermal stimulation as well as water flow erosion, warm brine injection provides three dimensionally connected channels in hydrate for subsequent mass transfer, improving CH 4 /CO 2 replacement in the deep layer of hydrate. CO 2 sequestration efficiency of the newly proposed method reaches 76.46%, and the maximum amounts of CH 4 recovery is nearly treble than that achieved by single CO 2 replacement method. Notably, a potential risk of secondary hydrate formation could occur upon the pressure surge and fluid migration attached to warm brine injection, which could be effectively alleviated by increasing salinity to destabilize hydrate lattices by reducing water activity. The gas production is insensitive to the injected heat as the significant heat loss during the transportation of injected brine in pipelines and thermal diffusion through boundaries. The introduction of free water increases the complexity of the reactions in hydrate reservoirs, and the formulation of brine injection regimes should be synergistically optimized based on energy harvest, energy efficiency and CO 2 sequestration. This work extends the previous knowledge on CH 4 /CO 2 replacement and shows important practical significance for future field studies of NGHs exploitation and CO 2 geological sequestration. [ABSTRACT FROM AUTHOR]

Schematic diagram for N 2 /CO 2 gas enrichment process during hydrate growth process. Blue sticks and spheres: N 2 in the gas phase; yellow spheres: CO 2 in the gas phase or hydrate phase; red sticks: hydrate seeds. [Display omitted] • Proper subcooling can improve the hydrate growth rate and final occupancy of CO 2 molecules. • Mass transfer process could impact the hydrate growth rate, with a higher pressure improving the concentrations of N 2 and CO 2 in the free water. • Higher pressure decreased the selectivity of CO 2 for 51262, and lower subcooling assisted CO 2 in entering 51262 cages easily. The climate system is changing and becoming warmer due to the consumption of fossil energy, which results in a large quantity of CO 2 emitted into the atmosphere. The hydrate formation process can encapsulate guest molecules in hydrate cages, enabling a promising storage of CO 2 in the form of hydrate under the seafloor. Here, we performed molecular dynamics (MD) simulations to validate the hydrate-based gas storage method for low-concentration flue gas. The direct phase method was applied at four target pressures to obtain the melting temperature of mixed gas hydrate in the presence of SI hydrate seeds that are fully occupied by CO 2 molecules. Hydrate growth simulations showed that a proper subcooling can improve the hydrate growth rate and final occupancy of CO 2 molecules in newly formed hydrate cages. The mass transfer process could impact the hydrate growth rate, with a higher pressure improving the concentrations of N 2 and CO 2 in the free water. This enhanced the hydrate growth at both 260 K and low subcooling temperatures. The influence of pressure and subcooling on cage selectivity presented a different tendency for CO 2 and N 2. A higher pressure decreased the selectivity of CO 2 for 51262, and lower subcooling assisted CO 2 in entering 51262 cages easily. Interestingly, the CO 2 occupancy at 260 K is larger than that of the simulations at the melting temperature. The results could be of help in revealing the behavior of case filling during hydrate formation from a gas mixture. [ABSTRACT FROM AUTHOR]