Knowledge of the kinetics of adsorption of CO2 and CH4 on shales is essential for the optimization of
the technique
of enhanced gas recovery by CO2 injection. In this paper,
the experiments of adsorption kinetics of CO2 and CH4 on marine Wufeng (WF) shale and continental Yanchang (YC)
shale at 318, 338, and 358 K over the pressure range of 3.0–8.0
MPa were conducted by a volumetric method. Results show that the adsorption
processes of CH4 and CO2 on the shales can be
described as an initial rapid adsorption stage and a slow sorption
stage. The unipore model can simulate the kinetics data of CO2 and CH4 well. The diffusion coefficient (D) of gas increases with the increase of pressure. High
temperatures will help to improve the diffusivities of CO2 and CH4. The order of magnitude of D of CO2 and CH4 on the two samples is 10–11 m2/s. The diffusion activation energies
(E
a) of CO2 and CH4 on YC shale are 3.37 and 10.15 kJ/mol, respectively, and E
a of CO2 and CH4 on WF
shale are 1.33 and 3.56 kJ/mol, respectively. The E
a value of CH4 greater than that of CO2 indicates that CH4 diffusion in shale formation
is more difficult and needs to jump a higher potential barrier. There
is a positive correlation of pressure with the adsorption rates of
CO2 and CH4. As the temperature enhances, the
gas adsorption rate reduces. The ratios of D of CO2, CH4, and N2 are 1.42:1.15:1.00 on
YC shale and 1.72:1.38:1.00 on WF shale. The adsorption rates of CO2, CH4, and N2 on the shales exhibit
a decreasing trend.