• Rother, G.; Ilton, E.S.; Wallacher, D.; Hauß, T.; Schaef, H.T.; Qafoku, O.; Rosso, K.M.; Felmy, A.R.; Krukowski, E.G.; Stack, A.G.; Grimm, N.; Bodnar, R.J.: CO2 Sorption to Subsingle Hydration Layer Montmorillonite Clay Studied by Excess Sorption and Neutron Diffraction Measurements. Environmental Science & Technology 47 (2013), p. 205-211

10.1021/es301382y

Abstract:
Geologic storage of CO2 requires that the caprock sealing thestorage rock is highly impermeable to CO2. Swelling clays, which are important components of caprocks, may interact with CO2 leading to volume change and potentially impacting the seal quality. The interactions of supercritical (sc) CO2 with Na saturated montmorillonite clay containing a subsingle layer of water in the interlayer region have been studied by sorption and neutron diffraction techniques.The excess sorption isotherms show maxima at bulk CO2 densities of ≈0.15 g/cm3, followed by an approximately linear decrease of excess sorption to zero and negative values with increasing CO2 bulk density. Neutron diffraction experiments on the same clay sample measured interlayer spacing and composition. The results show that limited amounts of CO2 are sorbed into the interlayer region, leading to depression of the interlayer peak intensity and an increase of the d(001) spacing by ca. 0.5 Å. The density of CO2 in the clay pores is relatively stable over a wide range of CO2 pressures at a given temperature, indicating the formation of a clay-CO2 phase. At the excess sorption maximum, increasing CO2 sorption with decreasing temperature is observed while the high-pressure sorption properties exhibit weak temperature dependence.