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Title: Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO 2 Intercalation Probed by XRD, NMR, and GCMD Simulations

Abstract

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 and NMR results. 13C NMR and simulations show that the average orientation of the intercalated CO2 is with their O-C-O axes parallel to the basal clay surface and that they undergo a rapid rotation about an axis perpendicular to the main molecular axis. The simulations show that the strength of the interaction between the exchangeablemore » cation and the clay structure dominates the intercalation energetics in dry scCO2.« less

Authors:
ORCiD logo; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [4];
  1. Department of Chemistry and Biochemistry, St. Mary’s College of Maryland, St. Mary’s City, Maryland 20686, United States
  2. Department of Chemical Engineering, University College London, London WC1E7JE, U.K.
  3. Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  4. Laboratoire SUBATECH (UMR 6457—Institut Mines-Télécom Atlantique, Université de Nantes, CNRS/IN2P3), 44307 Nantes, France
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1502419
Report Number(s):
PNNL-SA-136310
Journal ID: ISSN 1932-7447
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., and Kirkpatrick, R. James. Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO 2 Intercalation Probed by XRD, NMR, and GCMD Simulations. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12270.
Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., & Kirkpatrick, R. James. Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO 2 Intercalation Probed by XRD, NMR, and GCMD Simulations. United States. doi:10.1021/acs.jpcc.7b12270.
Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., and Kirkpatrick, R. James. Tue . "Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO 2 Intercalation Probed by XRD, NMR, and GCMD Simulations". United States. doi:10.1021/acs.jpcc.7b12270.
@article{osti_1502419,
title = {Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO 2 Intercalation Probed by XRD, NMR, and GCMD Simulations},
author = {Loganathan, Narasimhan and Bowers, Geoffrey M. and Yazaydin, A. Ozgur and Schaef, H. Todd and Loring, John S. and Kalinichev, Andrey G. and Kirkpatrick, R. James},
abstractNote = {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 and NMR results. 13C NMR and simulations show that the average orientation of the intercalated CO2 is with their O-C-O axes parallel to the basal clay surface and that they undergo a rapid rotation about an axis perpendicular to the main molecular axis. The simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2.},
doi = {10.1021/acs.jpcc.7b12270},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 8,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}