CO2 Intercalation Research Articles

Control of the Structural Charge Distribution and Hydration State upon Intercalation of CO2 into Expansive Clay Interlayers

Numerous experimental investigations indicated that expansive clays such as montmorillonite can intercalate CO2 preferentially into their interlayers and therefore potentially act as a material for CO2 separation, capture, and storage. However, an understanding of the energy-structure relationship during the intercalation of CO2 into clay interlayers remains elusive. Here, we use metadynamics molecular dynamics simulations to elucidate the energy landscape associated with CO2 intercalation. Our free energy calculations indicate that CO2 favorably partitions into nanoconfined water in clay interlayers from a gas phase, leading to an increase in the CO2/H2O ratio in clay interlayers as compared to that in bulk water. CO2 molecules prefer to be located at the centers of charge-neutral hydrophobic siloxane rings, whereas interlayer spaces close to structural charges tend to avoid CO2 intercalation. The structural charge distribution significantly affects the amount of CO2 intercalated in the interlayers. These results provide a mechanistic understanding of CO2 intercalation in clays for CO2 separation, capture, and storage.

Influence of CO2 on Nanoconfined Water in a Clay Mineral

Developing new technologies for carbon sequestration and long-term carbon storage is important. Clay minerals are interesting in this context as they are low-cost, naturally abundant, can adsorb considerable amounts of CO2, and are present in storage sites for anthropogenic carbon. Here, to better understand the intercalation mechanisms of CO2 in dehydrated and hydrated synthetic Na-fluorohectorite clay, we have combined powder X-ray diffraction, inelastic and quasi-elastic neutron scattering, and density functional theory calculations. For dehydrated Na-fluorohectorite, we observe no crystalline swelling or spectroscopic changes in response to CO2, whereas for the hydrated case, damping of the librational modes related to the intercalated water was clearly observed. These findings suggest the formation of a more disordered water coordination in the interlayer associated with highly confined water molecules. From the simulations, we conclude that intercalated water molecules decrease the layer–layer cohesion energy and create physical space for CO2 intercalation. Furthermore, we confirm that interlayer confinement reduces the Na+ hydration number when compared to that in bulk aqueous water, which may allow for proton transfer and hydroxide formation followed by CO2 adsorption in the form of carbonates. The experimental results are discussed in the context of previous and present observations on, a similar smectite, Ni-fluorohectorite, for which it is established that CO2 attaches to the edge of nickel hydroxide islands present in the interlayer.

Scalable production of high-quality exfoliated graphene using mechanical milling in conjugation with supercritical CO2

The progress of graphene (GNs) exfoliation by ball milling from laboratory to commercial scale is still facing formidable challenges due to the extremely long milling process, toxic auxiliaries, dispersant, and complex post-purification steps. Herein, a highly-efficient and green exfoliation process using the synergetic effect of high-energy planetary ball-milling coupled with supercritical carbon dioxide (scCO2) was developed. The collaborative effect of high-shear force (SF) of planetary ball mill and CO2 intercalation through the graphite crevices increased the yield of GNs up to 59% under the optimized parameters. The exfoliated GNs flakes were highly dispersible in different organic solvents (eg. N-methyl pyrrolidone, dimethylformamide, and ethanol) and ≈71.32 % of GNs were less than 5 layers. The exfoliated GNs revealed a large graphitic domain and micrometer-scale lateral dimension. The electrical conductivity (σ) of the GNs film was 5.76 × 105 S·m−1. Also, the in-plane and through-plane σ of the GNs/high-density-polyethylene (GNs/HDPE) nanocomposite achieved 3.59 and 1.37 S·m−1 at 3% (weight/weight, w/w) of GNs loading amount respectively, encompassing the excellent viability of GNs in a wide range of applications. This new process holds a strong potential to overcome the drawbacks of GNs exfoliation by the common ball milling procedure and could boost the commercial scale-up opportunity.

Synergistic Coupling of CO2 and H2O during Expansion of Clays in Supercritical CO2-CH4 Fluid Mixtures.

We used IR and XRD, with supporting theoretical calculations, to investigate the swelling behavior of Na+-, NH4+-, and Cs+-montmorillonites (SWy-2) in supercritical fluid mixtures of H2O, CO2, and CH4. Building on our prior work with Na-clay that demonstrated that H2O facilitated CO2 intercalation at relatively low RH, here we show that increasing CO2/CH4 ratios promote H2O intercalation and swelling of the Na-clay at progressively lower RH. In contrast to the Na-clay, CO2 intercalated and expanded the Cs-clay even in the absence of H2O, while increasing fluid CO2/CH4 ratios inhibited H2O intercalation. The NH4-clay displayed intermediate behavior. By comparing changes in the HOH bending vibration of H2O intercalated in the Cs-, NH4-, and Na-clays, we posit that CO2 facilitated expansion of the Na-clay by participating in outer-sphere solvation of Na+ and by disrupting the H-bond network of intercalated H2O. In no case did the pure CH4 fluid induce expansion. Our experimental data can benchmark modeling studies aimed at predicting clay expansion in humidified fluids with varying ratios of CO2 and CH4 in real reservoir systems with implications for enhanced hydrocarbon recovery and CO2 storage in subsurface environments.

Tuning the Hydrophobicity of Layer-Structure Silicates To Promote Adsorption of Nonaqueous Fluids: Effects of F– for OH– Substitution on CO2 Partitioning into Smectite Interlayers

The intercalation of non-aqueous fluids in the nanopores of organic and inorganic materials is of significant interest, particularly in the energy science community. Recently, XRD and computational modeling results have shown that structural F- for OH- substitution in layered silicates makes them more hydrophobic. Here, we use Grand Canonical Molecular Dynamics (GCMD) calculations to investigate how increasing the F-/(F-+OH-) ratio of a prototypical layered silicate (the smectite Na-hectorite) impacts the intercalation behavior of CO2 and H2O at elevated temperature and pressure. At the conditions of this study (T = 323 K, P = 90 bar, water-saturated CO2), increasing F- for OH- substitution causes decreasing total CO2+H2O intercalation, increasing CO2/(CO2+H2O) ratios in the interlayer galleries, and an increasing energy barrier to CO2 and H2O intercalation. CO2 intercalation is greatest at monolayer basal spacings, and the results support the idea that with Na+ as the exchangeable cation the interlayers must be propped open by some H2O molecules to allow CO2 to enter the interlayer galleries. The computed immersion energies suggest that the bilayer or a more expanded structure is the stable state under these conditions, in agreement with experimental results, and that the basal spacings of the minimum energy 2L structures increase with increasing F- for OH- substitution. These results are consistent with a wide range of experimental data for smectites at ambient conditions and elevated pressures and temperatures and suggest that F- for OH- substitution in conjunction with reduced structural charge and exchange with large, low charge cations may increase the ability of smectite minerals to incorporate hydrophobic species such as CH4, CO2, H2, and other organic compounds.

Competitive Adsorption of H2O and CO2 in 2-Dimensional Nanoconfinement: GCMD Simulations of Cs- and Ca-Hectorites

The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological carbon sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge-balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using grand canonical molecular dynamics methods. The results show that the intercalation behavior is greatly different for the cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than for cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+, the presence of a sub-monolayer of H2O is ...

Exfoliation of graphite in CO2 expanded organic solvents combined with low speed shear mixing

A simple and effective method of producing pristine graphene sheets was investigated in this study. Natural graphite flakes were exfoliated in CO2 expanded N-methylpyrrolidone with a low speed agitation of 1000 rpm followed by 30min sonication. Few-layer graphene were obtained with the concentration of 0.0576 mg/mL after centrifugation at 4000 rpm for 30min. More than 90% of the product were two or three-layer graphene and 12–38% were even monolayer. In addition, ethylene glycol and ethanol were also proved to be effective solvents with the assistance of CO2 intercalation, but they were not good solvents for the exfoliation in the subsequent sonication process. Finally, Agitation time, the system pressure and temperature were systemically investigated to find out more appropriate parameters for the production.

Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations

In situ X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) experiments combined with molecular dynamics simulations using the grand canonical ensemble [grand canonical molecular dynamics (GCMD)] show that the cation size, charge, and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical scCO2 (scCO2) under conditions relevant to petroleum reservoirs and geological CO2 sequestration conditions. The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with small ionic radii and high solvation energies (e.g., Na+ and Ca2+) does not intercalate CO2 and that the fully collapsed interlayer structure is the most energetically stable configuration. With Cs+ and Ba2+, the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+, there is not even an energy barrier for CO2 intercalation, in agreement with the XRD a...

Oedometric Small-Angle Neutron Scattering: In Situ Observation of Nanopore Structure During Bentonite Consolidation and Swelling in Dry and Hydrous CO2 Environments.

Results of oedometric consolidation experiments linked with small-angle neutron scattering (SANS) measurements are presented, using SWy-2 Wyoming bentonite clay in dry and water-bearing N2 and CO2 atmospheres. Oedometric SANS involves deforming a porous sample under uniaxial strain conditions with applied axial force and internal pore pressure control, and combines with SANS for in situ observation of pore structure evolution and interaction. Scattering from both interlayer (clay intra-aggregate) and free (interaggregate) pores is observed, showing decreasing pore size with dry consolidation and interactions between interlayer and free pore types with swelling and consolidation. Introduction of dry liquid CO2 at zero effective stress (axial stress minus pore pressure) produces large shifts in interlayer scatterers, but is reversible back to pre-CO2 levels upon decreasing pore pressure and increasing effective stress. Introduction of wet liquid CO2, conversely, produces large but irreversible changes in interlayer scatterers, which are interpreted to be the combined result of CO2 and H2O intercalation under hydrostatic conditions, but which diminish with application of effective pressure and consolidation to higher bentonite dry densities. Consideration of CO2 intercalation in smectite-bearing CO2 caprocks needs to include effects of both water and nonhydrostatic stress.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2.

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well-known to be systematically correlated with the hydration free energy of the interlayer cation, particularly in environments dominated by nonpolar solvents (i.e., CO2), uptake into the interlayer is not well-understood. Using novel high-pressure capabilities, we investigated the interaction of dry supercritical CO2 with Na-, NH4-, and Cs-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H2O and that cation solvation energies in CO2 suggest a stronger interaction with Na, both the NH4- and Cs-clays readily absorbed CO2 and expanded, while the Na-clay did not. The apparent inertness of the Na-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na-clay but little or no energy barrier for the NH4- and Cs-clays. Indeed, the combination of experiment and theory clearly demonstrate that CO2 intercalation of Na-montmorillonite clays is prohibited in the absence of H2O. Consequently, we have shown for the first time that in the presence of a low dielectric constant, gas swelling depends more on the strength of the interaction between the interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicate swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage, and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semipermeable reactive barriers.

Changes in micromechanical properties of Na-montmorillonite caused by CO2/H2O sorption

CO2/H2O intercalation causes changes in the elastic mechanical properties of clay. This phenomenon is critical to geologic carbon sequestration (GCS) and enhancing oil rate (EOR) via CO2 adsorption. In this work, the elastic stiffness and hydrostatic mechanical behavior of Na-montmorillonite (MMT) exposure to variable component of CO2/H2O mixture are investigated using combinations of Monte Carlo and Molecular Dynamic methods. In the hydrostatic test simulation of 1W and 2W hydrated state, volume and basal spacing d001 linearly decrease with the increasing hydrostatic pressure. Moreover, gradients of 1W hydrated state are smaller than that of the gradients of 2W hydrated state. The linear gradient is related to the elastic modulus. Therefore higher hydrated state results in softer structure. Additionally, the yielding bulk modulus linearly decreases with the pressure. The decreasing gradient almost keeps at a constant of 1.0GPa/GPa with variable component of CO2/H2O. At the super critical condition of CO2 (P=0.01GPa, T=304.5K), the elastic stiffness fluctuates with the variable component of H2O/CO2. CO2 intercalation strongly affects the out-of-plane elastic stiffness while has little influence on the in-plane stiffness.

Molecular Understanding of CO2 and H2O in a Montmorillonite Clay Interlayer under CO2 Geological Sequestration Conditions

Grand canonical Monte Carlo (GCMC) simulations are carried out to investigate a supercritical carbon dioxide (scCO2)-water mixture in the Na-montmorillonite clay interlayer under typical CO2 geological sequestration conditions (T = 323 K, P = 90 bar and T = 348 K, P = 130 bar). The stable clay interlayer distances at different relative humidity (RH) are determined based on the normal pressure and free energy curves of the CO2–H2O–Na+ complex in the montmorillonite clay interlayer. Simulation results show that stable monolayer hydrates (1W) with a basal spacing around 12 A are formed at RH = 30–60%. As RH is increased to 70% and above, bilayer CO2–H2O mixtures with a basal spacing around 15–16 A (2W) are more stable. In general, the CO2 intercalation process is strongly influenced by RH. While a high relative humidity facilitates water molecules entering the clay interlayer, it nonetheless decreases CO2 intercalations. The sorbed H2O concentrations from our simulations compare remarkably well with the in s...

Microstructural response of variably hydrated Ca-rich montmorillonite to supercritical CO2.

First-principles molecular dynamics simulations were carried out to explore the mechanistic and thermodynamic ramifications of the exposure of variably hydrated Ca-rich montmorillonites to supercritical CO2 and CO2-SO2 mixtures under geologic storage conditions. In sub- to single-hydrated systems (≤ 1W), CO2 intercalation causes interlamellar expansion of 8-12%, while systems transitioning to 2W may undergo contraction (∼ 7%) or remain almost unchanged. When compared to ∼2W hydration state, structural analysis of the ≤ 1W systems, reveals more Ca-CO2 contacts and partial transition to vertically confined CO2 molecules. Infrared spectra and projected vibrational frequency analysis imply that intercalated Ca-bound CO2 are vibrationally constrained and contribute to the higher frequencies of the asymmetric stretch band. Reduced diffusion coefficients of intercalated H2O and CO2 (10(-6)-10(-7) cm(2)/s) indicate that Ca-montmorillonites in ∼ 1W hydration states can be more efficient in capturing CO2. Simulations including SO2 imply that ∼ 0.66 mmol SO2/g clay can be intercalated without other significant structural changes. SO2 is likely to divert H2O away from the cations, promoting Ca-CO2 interactions and CO2 capture by further reducing CO2 diffusion (10(-8) cm(2)/s). Vibrational bands at ∼ 1267 or 1155 cm(-1) may be used to identify the chemical state (oxidation states +4 or +6, respectively) and the fate of sulfur contaminants.

In situ study of CO₂ and H₂O partitioning between Na-montmorillonite and variably wet supercritical carbon dioxide.

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.

CO2 Utilization and Storage in Shale Gas Reservoirs: Experimental Results and Economic Impacts

Natural gas is considered a cleaner and lower-emission fuel than coal, and its high abundance from advanced drilling techniques has positioned natural gas as a major alternative energy source for the U.S. However, each ton of CO2 emitted from any type of fossil fuel combustion will continue to increase global atmospheric concentrations. One unique approach to reducing anthropogenic CO2 emissions involves coupling CO2 based enhanced gas recovery (EGR) operations in depleted shale gas reservoirs with long-term CO2 storage operations. In this paper, we report unique findings about the interactions between important shale minerals and sorbing gases (CH4 and CO2) and associated economic consequences. Where enhanced condensation of CO2 followed by desorption on clay surface is observed under supercritical conditions, a linear sorption profile emerges for CH4. Volumetric changes to montmorillonites occur during exposure to CO2. Theory-based simulations identify interactions with interlayer cations as energetically favorable for CO2 intercalation. In contrast, experimental evidence suggests CH4 does not occupy the interlayer and has only the propensity for surface adsorption. Mixed CH4:CO2 gas systems, where CH4 concentrations prevail, indicate preferential CO2 sorption as determined by in situ infrared spectroscopy and X-ray diffraction techniques. Collectively, these laboratory studies combined with a cost-based economic analysis provide a basis for identifying favorable CO2-EOR opportunities in previously fractured shale gas reservoirs approaching final stages of primary gas production. Moreover, utilization of site-specific laboratory measurements in reservoir simulators provides insight into optimum injection strategies for maximizing CH4/CO2 exchange rates to obtain peak natural gas production.

Molecular Dynamics Simulations of Carbon Dioxide Intercalation in Hydrated Na-Montmorillonite

Molecular dynamics simulations using classical force fields were carried out to study the structural and transport properties of clay mineral–water–CO2 systems at pressure and temperature relevant to geological carbon storage. The simulations show that the degree of swelling caused by intercalation of CO2 strongly depends on the initial water content in the interlayer space and that CO2 intercalation stimulates inner-sphere adsorption of the positively charged interlayer ions on the internal clay surfaces, which modifies the wetting properties of the surfaces. DFT-based molecular dynamics simulations were used to interpret the origin of the observed shift in the asymmetric stretch vibration of CO2 trapped in montmorillonite. The origin of the shift is attributed to the electric field effects on the CO2 molecules induced by the water molecules.

Clay Hydration/dehydration in Dry to Water-saturated Supercritical CO2: Implications for Caprock Integrity

Injection of supercritical CO2 (scCO2) for the geologic storage of carbon dioxide will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water- saturated scCO2. Wet scCO2 is highly reactive and capable of carbonating and hydrating certain minerals, whereas anhydrous scCO2 can dehydrate water-containing minerals. Because these geochemical processes affect solid volume and thus porosity and permeability, they have the potential to affect the long-term integrity of the caprock seal. In this study, we investigate the swelling and shrinkage of an expandable clay found in caprock formations, montmorillonite (Ca-STx-1), when exposed to variable water-content scCO2 at 50°C and 90bar using a combination of in situ probes, including X-ray diffraction (XRD), in situ magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), and in situ attenuated total reflection infrared spectroscopy (ATR-IR). We show that the extent of montmorillonite clay swelling/shrinkage is dependent not only on water hydration/dehydration, but also on CO2 intercalation reactions. Our results also suggest a competition between water and CO2 for interlayer residency where increasing concentrations of intercalated water lead to decreasing concentrations of intercalated CO2. Overall, this paper demonstrates the types of measurements required to develop fundamental knowledge that will enhance modeling efforts and reduce risks associated with subsurface storage of CO2.

X-ray Studies of Carbon Dioxide Intercalation in Na-Fluorohectorite Clay at Near-Ambient Conditions

We show experimentally that gaseous CO(2) intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite at conditions not too far from ambient. The mean interlayer repetition distance of the clay when CO(2) is intercalated is found to be 12.5 Å for the conditions -20 °C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that observed in the dehydrated-monohydrated transition for H(2)O, but the possibility of water intercalation is ruled out by a careful analysis of the experimental conditions and repeating the measurements exposing the clay to nitrogen gas. The dynamics of the process is observed to be dependent on the pressure, with a higher intercalation rate at increased pressure. The rate of CO(2) intercalation at the studied conditions is found to be several orders of magnitude slower than the intercalation rate of water or humidity at ambient pressure and temperature.