Influence of the initial CH4-hydrate system properties on CO2 capture kinetics

•Exchange kinetic in CH4-hydrates using CO2 or CO2-N2 gas.•Impact of the initial CH4-hydrate system properties on the kinetic.•Structure, cage occupancy and phase composition monitored by Raman spectroscopy.•Quantitative and qualitative estimates of factors influencing the kinetic. Recovering methane from natural gas hydrate deposits using carbon dioxide injection is currently of great environmental and energetic interest as it shows potential for producing an energy resource while mitigating CO2 emissions through CO2 sequestration. This work investigates the exchange kinetic between CH4 and CO2 (or CO2-N2(v)) in synthetic hydrates, with an emphasis on the impact of CH4 hydrate formation conditions (e.g. driving force Δp) on the subsequent exchange reactions. Different driving forces Δp are utilized and show that the exchange kinetic is improved by a factor of ~3 when the exchange is performed with low Δp CH4 hydrates, for which there is a higher relative amount of free H2O(liq) (277 K); the kinetic is further improved when stirring is applied. Isobaric CH4 hydrates exhibit a fast primary hydrate dissociation and CH4 release, followed by a slower exchange kinetic, possibly limited by solid-state exchange diffusion or secondary CO2-rich hydrate formation within the stability field of CH4 hydrates. Upon exposure to a mixed CO2-N2(v) gas stream, secondary hydrate production is governed by the effective Δp remaining after dissolution of the gas mixture, and results in an even slower exchange reaction rate. These results may help optimizing recovery processes in field trial experiments, where both hydrates and liquid water coexist, and aid in predicting the risk of geo-hazards induced by unstable secondary hydrate formation. Furthermore, the exchange kinetic dependencies highlighted here are important as they affect the overall energy efficiency and energy cost of CH4 recovery processes in gas hydrate field trials.