Adsorption and capillary condensation in porous media as a function of the chemical potential of water in carbon dioxide

Heath, Jason E.; Bryan, Charles R.; Matteo, Edward N; Dewers, Thomas; Wang, Yifeng; Sallaberry, Cédric J.

doi:10.1002/2013wr013728

Cited by 18 publications

(18 citation statements)

References 43 publications

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“…It should be noted that these thicknesses are averages, and that capillary forces could lead to heterogeneities in the water film thickness, such as by forming thicker water films at the contact points between forsterite particles and thinner water films elsewhere. 48 Future work will investigate possible roles that carbonate surface complexes may play with regard to nucleation and growth of magnesite. Nucleation of magnesite might occur more readily on a forsterite surface covered with carbonate surface complexes.…”

Section: Discussionmentioning

confidence: 99%

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

et al. 2015

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Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and postreaction samples were examined by ex situ techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), focused ion beam transmission electron microscopy (FIB-TEM), thermal gravimetric analysis mass spectrometry (TGA-MS), and magic angle spinning nuclear magnetic resonance (MAS NMR). Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 μmol/m(2). Above this concentration and up to 76 μmol/m(2), monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 μmol/m(2), crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

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Section: Discussionmentioning

confidence: 99%

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

et al. 2015

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“…This could be due to capillary condensation in the mesopore system of the coal or the pore‐filling phenomenon which occurs in nanopores . In addition, since the coal sample is dried naturally, the presence of residual water vapor inside the coal may also contribute to the carbon dioxide condensation . Therefore, the conventional sorption equilibrium determination approach cannot be applied in these stages.…”

Section: Discussionmentioning

confidence: 99%

Isothermal adsorption kinetics properties of carbon dioxide in crushed coal

Tang

Ripepi

Gilliland

2015

Greenhouse Gas Sci Technol

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Understanding the dynamic response of coal to carbon dioxide sorption is crucial for optimizing carbon dioxide sequestration in unmineable coal seams and enhanced coalbed methane recovery. In order to explore the adsorption kinetics of carbon dioxide in coal, 15 isothermal adsorption tests were conducted on bituminous and sub‐bituminous coals at 50°C for increasing equilibrium pressures (up to 4 MPa). The pseudo‐second order (PSO) model is introduced to approximate the carbon dioxide sorption kinetics in coal, and the kinetics properties are then investigated via the PSO model. The linear relationship between (t/q) and (t) is validated and confirmed with a high correlation coefficient (>99%). The kinetics parameter, k2, decreases with both increasing equilibrium sorption pressure and increasing pressure difference. The sorption equilibrium content, Qe, in each sorption stage depends on both the final equilibrium pressure and the pressure difference. Based on the relationship between sorption content and time, the sorption content for different pressure ranges is predicted using different time intervals. The analysis indicates that the adsorption process for carbon dioxide in coal is a combination of both bulk diffusion‐controlled and surface interaction‐controlled processes; the former dominates the initial stage while the latter controls the majority of the overall process. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd

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“…In situations of multiphase flow, capillary condensation of water films at crack tips can alter the local chemistry of the crack tip environment in glass, promoting accelerated growth rates (Ciccotti, ; Ciccotti et al, ). In the Earth's subsurface, such a mechanism may be important for considerations of carbon storage (Heath et al, ), as condensed water films from supercritical carbon dioxide may partition highly reactive acid gases and have a lower pH than bulk pore solutions.…”

Section: Why Chemistry Is Important In Understanding Formation and Evmentioning

confidence: 99%

The Role of Chemistry in Fracture Pattern Development and Opportunities to Advance Interpretations of Geological Materials

Laubach

Lander²,

Criscenti

et al. 2019

Reviews of Geophysics

228

106

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Fracture pattern development has been a challenging area of research in the Earth sciences for more than 100 years. Much has been learned about the spatial and temporal complexity inherent to these systems, but severe challenges remain. Future advances will require new approaches. Chemical processes play a larger role in opening‐mode fracture pattern development than has hitherto been appreciated. This review examines relationships between mechanical and geochemical processes that influence the fracture patterns recorded in natural settings. For fractures formed in diagenetic settings (~50 to 200 °C), we review evidence of chemical reactions in fractures and show how a chemical perspective helps solve problems in fracture analysis. We also outline impediments to subsurface pattern measurement and interpretation, assess implications of discoveries in fracture history reconstruction for process‐based models, review models of fracture cementation and chemically assisted fracture growth, and discuss promising paths for future work. To accurately predict the mechanical and fluid flow properties of fracture systems, a processes‐based approach is needed. Progress is possible using observational, experimental, and modeling approaches that view fracture patterns and properties as the result of coupled mechanical and chemical processes. A critical area is reconstructing patterns through time. Such data sets are essential for developing and testing predictive models. Other topics that need work include models of crystal growth and dissolution rates under geological conditions, cement mechanical effects, and subcritical crack propagation. Advances in machine learning and 3‐D imaging present opportunities for a mechanistic understanding of fracture formation and development, enabling prediction of spatial and temporal complexity over geologic timescales. Geophysical research with a chemical perspective is needed to correctly identify and interpret fractures from geophysical measurements during site characterization and monitoring of subsurface engineering activities.

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Adsorption and capillary condensation in porous media as a function of the chemical potential of water in carbon dioxide

Cited by 18 publications

References 43 publications

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

Isothermal adsorption kinetics properties of carbon dioxide in crushed coal

The Role of Chemistry in Fracture Pattern Development and Opportunities to Advance Interpretations of Geological Materials

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