[1] Flood basalts are a potentially important host medium for geologic sequestration of anthropogenic CO 2 . Most lava flows have flow tops that are porous and permeable and have enormous capacity for storage of CO 2 . Interbedded sediment layers and dense low-permeability basalt rock overlying sequential flows may act as effective seals allowing time for mineralization reactions to occur. Laboratory experiments confirm relatively rapid chemical reaction of CO 2 -saturated pore water with basalts to form stable carbonate minerals. Calculations suggest a sufficiently short time frame for onset of carbonate precipitation after CO 2 injection that verification of in situ mineralization rates appears feasible in field pilot studies. If proven viable, major flood basalts in the United States and India would provide significant additional CO 2 storage capacity and additional geologic sequestration options in certain regions where more conventional storage options are limited.
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.
This paper explores the molecular-scale interactions between CO2 and the representative smectite mineral hectorite under supercritical conditions (90 bar, 50 °C) using novel in situ X-ray diffraction (XRD), infrared (IR) spectroscopy, and magic angle spinning (MAS) nuclear magnetic resonance (NMR) techniques. Particular emphasis is placed on understanding the roles of the smectite charge balancing cation (CBC) and H2O in these interactions. The data show that supercritical CO2 (scCO2) can be adsorbed on external surfaces and in the confined interlayer spaces of hectorite at 50 °C and 90 bar, with the uptake of CO2 into the interlayer favored at low H2O content and when the basal spacing is similar to a monolayer hydrate of hectorite (1WL, ∼12.5 Å). These results are in agreement with published spectroscopic and molecular modeling data for the related smectite Na-montmorillonite. Charge balancing cations with small radii, large hydration energies, and low polarizabilities tend to scavenge H2O from humid scCO2 or retain the H2O they held before scCO2 exposure, swelling spontaneously to a bilayer hydrate (2WL) dominated state that largely prevents CO2-ion interactions and influences the extent of CO2 intercalation into the interlayer. In contrast, ions with large radii, low hydration energies, and large polarizabilities more readily form close associations with CO2 with the energetics enabling coexistence of CO2 and H2O in the interlayer over a wide range of scCO2 humidities. Integrating our results with those from molecular dynamics simulations of wet CO2-bearing montmorillonites suggest that adsorbed CO2 in 1WL-type interlayers is oriented with its long axis parallel to the clay sheets and experiences dynamics dominated by anisotropic rotation about the axis perpendicular to the CO2 long axis at rates of at least ∼105 Hz. If appreciable CO2 is adsorbed in 2WL-type interlayers, it must experience a mean orientation and dynamic averaging affects that mimic the 1WL-type adsorption environment. External surface adsorbed CO2 is dynamically similar to the 1WL case, but the CO2 long axis samples a larger range of orientations with respect to the smectite surface and adopts a different mean angle between the long axis and the smectite surface. Our data also suggest that equilibrating hectorite with a large volume of scCO2 at 50 °C and 90 bar leads to interlayer dehydration, with the extent of dehydration correlating with the hydrophilicity of the CBC.
Expandable clays such as montmorillonite have interlayer exchange sites whose hydration state can be systematically varied from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO 2 to both mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. In this study, the partitioning of CO 2 a n d H 2 O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO 2 (scCO 2 ) was investigated using in situ X-ray diffraction (HXRD), infrared (IR) spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H 2 O and CO 2 concentrations as a function of percent H 2 O saturation in scCO 2 . Intercalation of CO 2 is inhibited when the clay is fully collapsed (dehydrated interlayer), peaks sharply with the introduction of some H 2 O and partial expansion of the interlayer region, and then decreases systematically with further hydration of the clay. This behavior is discussed in the context of recent theoretical calculations of the montmorillonite H 2 O-CO 2 system.
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.
Carbonation reactions are central to the prospect of CO(2) trapping by mineralization in geologic reservoirs. In contrast to the relevant aqueous-mediated reactions, little is known about the propensity for carbonation in the key partner fluid: supercritical carbon dioxide containing dissolved water ("wet" scCO(2)). We employed in situ mid-infrared spectroscopy to follow the reaction of a model silicate mineral (forsterite, Mg(2)SiO(4)) for 24 h with wet scCO(2) at 50 °C and 180 atm. The results show a dramatic dependence of reactivity on water concentration and the presence of liquid water on the forsterite particles. Exposure to neat scCO(2) showed no detectable carbonation reaction. At 47% and 81% water saturation, an Ångstrom-thick liquid-like water film was detected on the forsterite particles and less than 1% of the forsterite transformed. Most of the reaction occurred within the first 3 h of exposure to the fluid. In experiments at 95% saturation and with an excess of water (36% above water saturation), a nanometer-thick water film was detected, and the carbonation reaction proceeded continuously with approximately 2% and 10% conversion, respectively. Our collective results suggest constitutive links between water concentration, water film formation, reaction rate and extent, and reaction products in wet scCO(2).
Reactions involving variably hydrated super critical CO(2) (scCO(2)) and a Na saturated dioctahedral smectite (Na-STX-1) were examined by in situ high-pressure X-ray diffraction at 50 °C and 90 bar, conditions that are relevant to long-term geologic storage of CO(2). Both hydration and dehydration reactions were rapid with appreciable reaction occurring in minutes and near steady state occurring within an hour. Hydration occurred stepwise as a function of increasing H(2)O in the system; 1W, 2W-3W, and >3W clay hydration states were stable from ~2-30%, ~31-55 < 64%, and ≥ ~71% H(2)O saturation in scCO(2), respectively. Exposure of sub 1W clay to anhydrous scCO(2) caused interlayer expansion, not contraction as expected for dehydration, suggesting that CO(2) intercalated the interlayer region of the sub 1W clay, which might provide a secondary trapping mechanism for CO(2). In contrast, control experiments using pressurized N(2) and similar initial conditions as in the scCO(2) study, showed little to no change in the d(001) spacing, or hydration states, of the clay. A salient implication for cap rock integrity is that clays can dehydrate when exposed to wet scCO(2). For example, a clay in the ~3W hydration state could collapse by ~3 Å in the c* direction, or ~15%, if exposed to scCO(2) at less than or equal to about 64% H(2)O saturation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.