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Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this study, in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy were used to investigate the swelling/shrinkage and H2O/CO2 sorption of Na(+)-exchanged montmorillonite, Na-SWy-2, as the clay is exposed to variably hydrated supercritical CO2 (scCO2) at 50 °C and 90 bar. Measured d001 values increased in stepwise fashion and sorbed H2O concentrations increased continuously with increasing percent H2O saturation in scCO2, closely following previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show H2O and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types of H2O and CO2 with distinct chemical environments. Based on the absorbance of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, the sorbed CO2 concentration increases dramatically at sorbed H2O concentrations from 0 to 4 mmol/g. Sorbed CO2 then sharply decreases as sorbed H2O increases from 4 to 10 mmol/g. With even higher sorbed H2O concentrations as saturation of H2O in scCO2 was approached, the concentration of sorbed CO2 decreased asymptotically. Two models, one involving space filling and the other a heterogeneous distribution of integral hydration states, are discussed as possible mechanisms for H2O and CO2 intercalations in montmorillonite. The swelling/shrinkage of montmorillonite could affect solid volume, porosity, and permeability of shales. Consequently, the results may aid predictions of shale caprock integrity in large-scale GCS as well as methane transmissivity in enhanced gas recovery operations.

The interaction of anhydrous supercritical CO(2) (scCO(2)) with both kaolinite and ~1W (i.e., close to but less than one layer of hydration) calcium-saturated montmorillonite was investigated under conditions relevant to geologic carbon sequestration (50 °C and 90 bar). The CO(2) molecular environment was probed in situ using a combination of three novel high-pressure techniques: X-ray diffraction, magic angle spinning nuclear magnetic resonance spectroscopy, and attenuated total reflection infrared spectroscopy. We report the first direct evidence that the expansion of montmorillonite under scCO(2) conditions is due to CO(2) migration into the interlayer. Intercalated CO(2) molecules are rotationally constrained and do not appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO(2) does not intercalate into kaolinite. The findings show that predicting the seal integrity of caprock will have complex dependence on clay mineralogy and hydration state.

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