Abstract
Abstract The CH 4 –flue gas replacement in naturally occurring gas hydrates has attracted significant attention due to its potential as a method of exploitation of clean energy and sequestration of CO 2 . In the replacement process, the thermodynamic and structural properties of the mixed gas hydrates are critical factors to predict the heat flow in the hydrate-bearing sediments and the heat required for hydrate dissociation, and to evaluate the CO 2 storage capacity of hydrate reservoirs. In this study, the 13 C NMR and gas composition analyses confirmed that the preferential enclathration of N 2 molecules in small 5 12 cages of structure I hydrates improved the extent of the CH 4 recovery. A high pressure micro-differential scanning calorimeter (HP μ -DSC) provided reliable hydrate stability conditions and heat of dissociation values in the porous silica gels after the replacement, which confirmed that CH 4 in the hydrates was successfully replaced with flue gas. A heat flow change associated with the dissociation and formation of hydrates was not noticeable during the CH 4 –flue gas replacement. Therefore, this study reveals that CH 4 –flue gas swapping occurs without structural transitions and significant hydrate dissociations.
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