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Abstract Geological storage of carbon dioxide (CO2) in depleted gas reservoirs represents a cost-effective solution to mitigate global carbon emissions. The surface chemistry of the reservoir rock, pressure, temperature, and moisture content are critical factors that determine the CO2 adsorption capacity and storage mechanisms. Shale-gas reservoirs are good candidates for this application. However, the interactions of CO2 and organic content still need further investigation. The objectives of this paper are to (i) experimentally investigate the effect of pressure and temperature on the CO2 adsorption capacity of activated carbon, (ii) quantify the nanoscale interfacial interactions between CO2 and the activated carbon surface using Monte Carlo molecular modeling, and (iii) quantify the correlation between the adsorption isotherms of activated carbon-CO2 system and the actual carbon dioxide adsorption on shale-gas rock at different temperatures and geochemical conditions. Activated carbon is used as a proxy for kerogen. The objectives aim at obtaining a better understanding of the behavior of CO2 injection and storage into shale-gas formations. We performed experimental measurements and Grand Canonical Monte Carlo (GCMC) simulations of CO2 adsorption onto activated carbon. The experimental work involved measurements of the high-pressure adsorption capacity of activated carbon using pure CO2 gas. Subsequently, we performed a series of GCMC simulations to calculate CO2 adsorption capacity on activated carbon to validate the experimental results. The simulated activated carbon structure consists of graphite sheets with a distance between the sheets equal to the average actual pore size of the activated carbon sample. Adsorption isotherms were calculated and modeled for each temperature value at various pressures. The adsorption of CO2 on activated carbon is favorable from the energy and kinetic point of view. This is due to the presence of a wide micro to meso pore sizes that can accommodate a large amount of CO2 particles. The results of the experimental work show that excess adsorption results for gas mixtures lie in between the results for pure components. The simulation results agree with the experimental measurements. The strength of CO2 adsorption depends on both surface chemistry and pore size of activated carbon. Once strong adsorption sites within nanoscale network are established, gas adsorption even at very low pressure is governed by pore width rather than chemical composition. The outcomes of this paper provides new insights about the parameters affecting CO2 adsorption and storage in shale-gas reservoirs, which is critical for developing standalone representative models for CO2 adsorption on pure organic carbon.
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Lattice Expansion and Ligand Twist during CO2 Adsorption in Flexible Cu Bipyridine Metal-Organic Frameworks
Flexible metal-organic frameworks (MOF) can show exceptional selectivity and capacity for adsorption of CO2. The incorporation of CO2 into flexible MOFs that have Cu2+ coordination centers and organic pillar ligands is accompanied by a distortion of the framework lattice arising from chemical interactions between these components and CO2 molecules. CO2 adsorption yields a reproducible lattice expansion that is enabled by the rotation of the pillar ligands. The structures of Cu2(pzdc)2(bpy) and Cu2(pzdc)2(bpe), CPL-2 and CPL-5, were evaluated using in situ synchrotron x-ray powder diffraction at room temperature at CO2 gas pressures up to 50 atm. The structural parameters exhibit hysteresis between pressurization and depressurization. The pore volume within CPL-2 and CPL-5 increases at elevated CO2 pressure due to a combination of the pillar ligand rotation and the overall expansion of the lattice. Volumetric CO2 adsorption measurements up to 50 atm reveal adsorption behavior consistent with the structural results, including a rapid uptake of CO2 at low pressure, saturation above 20 atm, and hysteresis evident as a retention of CO2 during depressurization. A significantly greater CO2 uptake is observed in CPL-5 in comparison with predictions based on CO2 pressure-induced expansion of the pore volume available for adsorption, indicating that the flexibility of the CPL structures is a key factor in enhancing adsorption capacity.
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- Award ID(s):
- 1720415
- PAR ID:
- 10190342
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- ISSN:
- 2050-7488
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0TA03298K
