Clay minerals abound in sedimentary formations and the interaction of reservoir gases with their sub-micron features has direct relevance to many geo-energy applications. The quantification of gas uptake over a broad range of pressures is key towards assessing the significance of these physical interactions on enhancing storage capacity and gas recovery. We report a systematic investigation of the sorption properties of three source clay minerals-Na-rich montmorillonite (SWy-2), illite-smectite mixed layer (ISCz-1), and illite (IMt-2)-using CO 2 and CH 4 up to 30 MPa at 25 to 115 • C. The textural characterization of the clays by gas physisorption indicates that micropores are only partly accessible to N 2 (77 K) and Ar (87 K), while larger uptakes are measured with CO 2 (273 K) in the presence of illite. The supercritical excess sorption experiments confirm these findings, while revealing differences in uptake capacities that originate from the clay-specific pore size distribution. The Lattice Density Functional Theory (LDFT) model describes accurately the measured sorption isotherms by using a distribution of properly weighted slit pores and clay-specific solid-fluid interaction energies, which agree with isosteric heats of adsorption obtained experimentally. The model indicates that the maximum degree of pore occupancy is universal to the three 1 clays and the two gases, and it depends solely on temperature, reaching values near unity at the critical temperature. These observations greatly support the model's predictive capability for estimating gas adsorption on clay-bearing rocks and sediments.
This paper reports the results of an international interlaboratory study led by the National Institute of Standards and Technology (NIST) on the measurement of high-pressure surface excess methane adsorption isotherms on NIST Reference Material RM 8850 (Zeolite Y), at 25 °C up to 7.5 MPa. Twenty laboratories participated in the study and contributed over one-hundred adsorption isotherms of methane on Zeolite Y. From these data, an empirical reference equation was determined, along with a 95% uncertainty interval (Uk=2). By requiring participants to replicate a high-pressure reference isotherm for carbon dioxide adsorption on NIST Reference Material RM 8852 (ZSM-5), this interlaboratory study also demonstrated the usefulness of reference isotherms in evaluating the performance of high-pressure adsorption experiments.
Understanding supercritical gas adsorption in porous carbons requires consistency between experimental measurements at representative conditions and theoretical adsorption models that correctly account for the solid's textural properties. We have measured unary CO 2 and CH 4 adsorption isotherms on a commercial mesoporous carbon up to 25 MPa at 40 • C, 60 • C and 80 • C. The experimental data are successfully described using a model based on the lattice Density Functional Theory (DFT) that has been newly developed for cylindrical pores and used alongside Ar (87K) physisorption to extract the representative pore sizes of the adsorbent. The agreement between model and experiments also includes important thermodynamic parameters, such as Henry constants and the isosteric heat of adsorption. The general applicability of our integrated workflow is validated by extending the analysis to a comprehensive literature data set on a microporous activated carbon. This comparison reveals the distinct pore-filling behaviour in micro-and mesopores at supercritical conditions, and highlights the limitations associated with using slit-pore models for the characterisation of porous carbons with significant amounts of mesoporosity. The lattice DFT represents a departure from simple adsorption models, such as the Langmuir equation, which cannot capture pore size dependent adsorption behaviour, and a practical alternative to molecular simulations, which are computationally expensive to implement.
The transport of chemically reactive fluids through fractured clay‐rich rocks is fundamental to many subsurface engineering technologies. Here, we present results of direct‐shear laboratory experiments with simultaneous imaging by X‐ray Computed Tomography in Opalinus claystone with subsequent fluid injection to unravel the interplay between mechanical fracture deformation, fluid sorption, and flow. Under constant radial stress (σc = 1.5 MPa), the average mechanical aperture trued¯CT increases with shear displacement. Upon brine injection, trued¯CT is reduced by 40% relative to initial conditions (trued¯CT0=140−250 μm) and fluid‐sorption induces a divergent displacement of the two sample halves (Δh = ±50 − 170 μm) quantified by digital image correlation. None of these changes are observed in a control experiment with decane, indicating that creep is subordinate to swelling in sealing the fracture. Swelling‐induced changes in permeability within the fracture are heterogeneous and largely affect the fracture flow field, as computed using numerical simulations.
Excess adsorption of CO 2 , CH 4 , N 2 , and H 2 on ZIF-8 was measured gravimetrically in the pressure range ranging from vacuum to 30 MPa at 298.15, 313.15, 333.15, 353.15, and 394.15 K using a magnetic suspension balance. The textural properties of the adsorbent materiali.e., skeletal density, surface area, pore volume, and pore-size distributionwere estimated by helium gravimetry and N 2 (77 K) physisorption. The adsorption isotherms were fitted with the Sips isotherm model and the virial equation, and the values of isosteric heat of adsorption and Henry constants for the gases were determined using the latter.
Gas adsorption at high pressures in porous solids is commonly quantified in terms of the excess amount adsorbed. Despite the wide spectrum of adsorbent morphologies available, the analysis of excess adsorption isotherms has mostly focused on microporous materials and the role of mesoporosity remains largely unexplored. Here, we present supercritical CO2 adsorption isotherms measured at $$T=308$$ T = 308 K in the pressure range $$p=0.02{-}21$$ p = 0.02 - 21 MPa on three adsorbents with distinct fractions of microporosity, $$\phi_2$$ ϕ 2 , namely a microporous metal-organic framework ($$\phi_2=70$$ ϕ 2 = 70 %), a micro-mesoporous zeolite ($$\phi_2=38$$ ϕ 2 = 38 %) and a mesoporous carbon ($$\phi_2<0.1$$ ϕ 2 < 0.1 %). The results are compared systematically in terms of excess and net adsorption relative to two distinct reference states–the space filled with gas in the presence/absence of adsorbent–that are defined from two separate experiments using helium as the probing gas. We discuss the inherent difficulties in extracting from the supercritical adsorption isotherms quantitative information on the properties of the adsorbed phase (its density or volume), because of the nonuniform distribution of the latter within and across the different classes of pore sizes. Yet, the data clearly reveal pore-size dependent adsorption behaviour, which can be used to identify characteristic types of isotherm and to complement the information obtained using the more traditional textural analysis by physisorption.
Understanding the long-term confinement of supercritical fluids in the clay pores of subsurface rocks is important for many geo-energy technologies, including geological CO2 storage. However, the adsorption properties of hydrated clay minerals remain largely uncertain because competitive adsorption experiments of supercritical fluids in the presence of water are difficult. Here, we report on the sorption properties of four source clay mineralsCa-rich montmorillonite (STx-1b), Na-rich montmorillonite (SWy-2), illite–smectite mixed layer (ISCz-1), and illite (IMt-2)for water at 20 °C up to relative humidity of 0.9. The measurements unveil the unsuitability of physisorption analysis by N2 (at 77 K) and Ar (at 87 K) gases to quantify the textural properties of clays because of their inability to probe the interlayers. We further measure the sorption of CO2 and CH4 on swelling STx-1b and nonswelling IMt-2, both in the absence (dehydrated at 200 °C) and the presence of sub-1W preadsorbed water (following dehydration) up to 170 bar at 50 °C. We observe enhanced sorption of CO2 and CH4 in STx-1b (50 and 65% increase at 30 bar relative to dry STx-1b, respectively), while their adsorption on IMt-2 remains unchanged, indicating the absence of competition with water. By describing the supercritical adsorption isotherms on hydrated STx-1b with the lattice density functional theory model, we estimate that the pore volume has expanded by approximately 6% through the formation of sub-nanometer pore space. By presenting a systematic approach of quantifying the smectite clay mineral’s hydrated state, this study provides an explanation for the conflicting literature observations of gas uptake capacities in the presence of water.
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