Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

Bowers, Geoffrey M.; Loring, John S.; Schaef, Herbert T.; Walter, Eric D.; Burton, Sarah D.; Hoyt, David W.; Cunniff, Sydney S.; Loganathan, Narasimhan; Kirkpatrick, Robert J.

doi:10.1021/acsearthspacechem.8b00039

Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

Journal Article · Thu Jul 19 04:00:00 EDT 2018 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.8b00039· OSTI ID:1560148

Bowers, Geoffrey M. ^[1]; Loring, John S. ^[2]; ^[2]; ^[2]; Burton, Sarah D. ^[2]; ^[2]; Cunniff, Sydney S. ^[2]; Loganathan, Narasimhan ^[3]; Kirkpatrick, Robert J. ^[4]

ALFRED UNIVERSITY
BATTELLE (PACIFIC NW LAB)
Michigan State University
MICHIGAN STATE UNIVERSITY

The results from novel in situ high-pressure nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and X-ray diffraction (XRD) investigation of the interaction of the smectite hectorite with variably wet supercritical methane (scCH4) at 90 bar and 323 K (hydrostatic conditions equivalent to ~1 km depth) show that CH4 occurs in the clay interlayers, in pores external to the individual clay particles, and as bulk fluid. The occupancy of each environment depends on the relative humidity (RH) of the CH4-rich fluid and the hydration energy and size of the charge-balancing cation. As RH increases, the fraction of interlayer and interparticle CH4 decreases, although with Cs+, addition of a small amount of H2O initially increases CH4 uptake. Maximum interlayer CH4 adsorption occurs when the mean basal spacing just permits methane intercalation (~11.5 Å) and never below this basal spacing. It is also higher with divalent cations than with monovalent cations. The data show that CH4 adsorption occurs predominantly via a weak dispersion interaction with the clay and that its intercalation occurs via a passive space-filling hydrophobic mechanism. The results suggest that, under reservoir conditions, smectite interlayers may provide a reservoir for CH4 under low-water conditions.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1560148

Report Number(s):: PNNL-SA-136218

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 7 Vol. 2

Country of Publication:: United States

Language:: English

References (54)

In Situ Infrared Spectroscopic Study of Brucite Carbonation in Dry to Water-Saturated Supercritical Carbon Dioxide Loring, John S.; Thompson, Christopher J.; Zhang, Changyong The Journal of Physical Chemistry A, Vol. 116, Issue 19 https://doi.org/10.1021/jp210020t	journal	May 2012
Water Structure and Dynamics in Smectites: X-ray Diffraction and ² H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan The Journal of Physical Chemistry C, Vol. 120, Issue 16 https://doi.org/10.1021/acs.jpcc.6b03431	journal	April 2016
High-pressure adsorption of methane on montmorillonite, kaolinite and illite Liu, Dong; Yuan, Peng; Liu, Hongmei Applied Clay Science, Vol. 85 https://doi.org/10.1016/j.clay.2013.09.009	journal	November 2013
Ionic hydration enthalpies Smith, Derek W. Journal of Chemical Education, Vol. 54, Issue 9 https://doi.org/10.1021/ed054p540	journal	September 1977
Molecular simulation of displacement of shale gas by carbon dioxide at different geological depths Zhang, Haibo; Cao, Dapeng Chemical Engineering Science, Vol. 156 https://doi.org/10.1016/j.ces.2016.09.002	journal	December 2016
In situ XRD study of Ca2+ saturated montmorillonite (STX-1) exposed to anhydrous and wet supercritical carbon dioxide Schaef, H. T.; Ilton, E. S.; Qafoku, O. International Journal of Greenhouse Gas Control, Vol. 6 https://doi.org/10.1016/j.ijggc.2011.11.001	journal	January 2012
Hydrocarbon Behavior at Nanoscale Interfaces Cole, D. R.; Ok, S.; Striolo, A. Reviews in Mineralogy and Geochemistry, Vol. 75, Issue 1 https://doi.org/10.2138/rmg.2013.75.16	journal	January 2013
In Situ Infrared Spectroscopic Study of Forsterite Carbonation in Wet Supercritical CO ₂ Loring, John S.; Thompson, Christopher J.; Wang, Zheming Environmental Science & Technology, Vol. 45, Issue 14 https://doi.org/10.1021/es201284e	journal	July 2011
Smectite fluorination and its impact on interlayer water content and structure: A way to fine tune the hydrophilicity of clay surfaces? Dazas, Baptiste; Lanson, Bruno; Breu, Josef Microporous and Mesoporous Materials, Vol. 181 https://doi.org/10.1016/j.micromeso.2013.07.032	journal	November 2013
Low-temperature cross-polarization/magic angle spinning carbon-13 NMR of solid methane hydrates: structure, cage occupancy, and hydration number Ripmeester, J. A.; Ratcliffe, C. I. The Journal of Physical Chemistry, Vol. 92, Issue 2 https://doi.org/10.1021/j100313a018	journal	January 1988
13C NMR spectroscopy of methane adsorbed in SAPO-11 molecular sieve Koskela, Tuomas; Ylihautala, Mika; Vaara, Juha Chemical Physics Letters, Vol. 261, Issue 4-5 https://doi.org/10.1016/0009-2614(96)00996-7	journal	October 1996
Structure, Energetics, and Dynamics of Smectite Clay Interlayer Hydration: Molecular Dynamics and Metadynamics Investigation of Na-Hectorite Morrow, Christin P.; Yazaydin, A. Özgür; Krishnan, Marimuthu The Journal of Physical Chemistry C, Vol. 117, Issue 10 https://doi.org/10.1021/jp312286g	journal	March 2013
Automated high-pressure titration system with in situ infrared spectroscopic detection Thompson, Christopher J.; Martin, Paul F.; Chen, Jeffrey Review of Scientific Instruments, Vol. 85, Issue 4 https://doi.org/10.1063/1.4870411	journal	April 2014
FT-IR investigation of methane adsorption on silica Wu, Jingang; Li, Shuben; Li, Guoqiang Applied Surface Science, Vol. 81, Issue 1 https://doi.org/10.1016/0169-4332(94)90083-3	journal	September 1994
Alkali Metal and H ₂ O Dynamics at the Smectite/Water Interface Bowers, Geoffrey M.; Singer, Jared W.; Bish, David L. The Journal of Physical Chemistry C, Vol. 115, Issue 47 https://doi.org/10.1021/jp2072167	journal	October 2011
Insights into silicate carbonation processes in water-bearing supercritical CO2 fluids Miller, Q. R. S.; Thompson, C. J.; Loring, J. S. International Journal of Greenhouse Gas Control, Vol. 15 https://doi.org/10.1016/j.ijggc.2013.02.005	journal	July 2013
CO ₂ Sorption to Subsingle Hydration Layer Montmorillonite Clay Studied by Excess Sorption and Neutron Diffraction Measurements Rother, Gernot; Ilton, Eugene S.; Wallacher, Dirk Environmental Science & Technology, Vol. 47, Issue 1 https://doi.org/10.1021/es301382y	journal	August 2012
In Situ Study of CO ₂ and H ₂ O Partitioning between Na–Montmorillonite and Variably Wet Supercritical Carbon Dioxide Loring, John S.; Ilton, Eugene S.; Chen, Jeffrey Langmuir, Vol. 30, Issue 21 https://doi.org/10.1021/la500682t	journal	May 2014
Recovery of Methane from Gas Hydrates Intercalated within Natural Sediments Using CO2 and a CO2/N2 Gas Mixture Koh, Dong-Yeun; Kang, Hyery; Kim, Dae-Ok ChemSusChem, Vol. 5, Issue 8 https://doi.org/10.1002/cssc.201100644	journal	June 2012
Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study Ok, Salim; Hoyt, David W.; Andersen, Amity Langmuir, Vol. 33, Issue 6 https://doi.org/10.1021/acs.langmuir.6b03590	journal	January 2017
Structural and dynamical relationships of Ca2+ and H2O in smectite/2H2O systems Bowers, G. M.; Singer, J. W.; Bish, D. L. American Mineralogist, Vol. 99, Issue 2-3 https://doi.org/10.2138/am.2014.4499	journal	February 2014
Determination of the average micropore diameter of an Illinois No. 6 coal by xenon-129 NMR Wernett, Patrick C.; Larsen, John W.; Yamada, Osamu Energy & Fuels, Vol. 4, Issue 4 https://doi.org/10.1021/ef00022a014	journal	July 1990
Methane and carbon dioxide adsorption in clay-like slit pores by Monte Carlo simulations Jin, Zhehui; Firoozabadi, Abbas Fluid Phase Equilibria, Vol. 360 https://doi.org/10.1016/j.fluid.2013.09.047	journal	December 2013
Mechanism of Adsorption and Desorption of Water Vapor by Homoionic Montmorillonites: 2. The Li+, Na+, K+, Rb+, and Cs+-Exchanged Forms Bérend, Isabelle Clays and Clay Minerals, Vol. 43, Issue 3 https://doi.org/10.1346/CCMN.1995.0430307	journal	January 1995
Operando MAS NMR Reaction Studies at High Temperatures and Pressures Walter, Eric D.; Qi, Long; Chamas, Ali The Journal of Physical Chemistry C, Vol. 122, Issue 15 https://doi.org/10.1021/acs.jpcc.7b11442	journal	January 2018
13 C NMR of methane in an AlPO 4 − 11 molecular sieve: Exchange effects and shielding anisotropy Koskela, Tuomas; Ylihautala, Mika; Jokisaari, Jukka Physical Review B, Vol. 58, Issue 22 https://doi.org/10.1103/PhysRevB.58.14833	journal	December 1998
Experimental investigation of main controls to methane adsorption in clay-rich rocks Ji, Liming; Zhang, Tongwei; Milliken, Kitty L. Applied Geochemistry, Vol. 27, Issue 12 https://doi.org/10.1016/j.apgeochem.2012.08.027	journal	December 2012
Shales at all scales: Exploring coupled processes in mudrocks Ilgen, Anastasia G.; Heath, Jason E.; Akkutlu, I. Yucel Earth-Science Reviews, Vol. 166 https://doi.org/10.1016/j.earscirev.2016.12.013	journal	March 2017
Mechanism of Adsorption and Desorption of Water Vapor by Homoionic Montmorillonite: 3. the Mg2+, Ca2+, Sr2+ and Ba2+ Exchanged Forms Cases, J. M. Clays and Clay Minerals, Vol. 45, Issue 1 https://doi.org/10.1346/CCMN.1997.0450102	journal	January 1997
Methane and Carbon Dioxide Adsorption on Illite Zhang, Junfang; Clennell, Michael B.; Liu, Keyu Energy & Fuels, Vol. 30, Issue 12 https://doi.org/10.1021/acs.energyfuels.6b01776	journal	November 2016
Molecular Simulations on the Structure and Dynamics of Water–Methane Fluids between Na-Montmorillonite Clay Surfaces at Elevated Temperature and Pressure Rao, Qi; Xiang, Yuan; Leng, Yongsheng The Journal of Physical Chemistry C, Vol. 117, Issue 27 https://doi.org/10.1021/jp403349p	journal	June 2013
In Situ ¹³ C and ²³ Na Magic Angle Spinning NMR Investigation of Supercritical CO ₂ Incorporation in Smectite–Natural Organic Matter Composites Bowers, Geoffrey M.; Hoyt, David W.; Burton, Sarah D. The Journal of Physical Chemistry C, Vol. 118, Issue 7 https://doi.org/10.1021/jp410535d	journal	February 2014
Supercritical Carbon Dioxide at Smectite Mineral–Water Interfaces: Molecular Dynamics and Adaptive Biasing Force Investigation of CO ₂ /H ₂ O Mixtures Nanoconfined in Na-Montmorillonite Sena, Mohan Maruthi; Morrow, Christin P.; Kirkpatrick, R. James Chemistry of Materials, Vol. 27, Issue 20 https://doi.org/10.1021/acs.chemmater.5b01855	journal	October 2015
In Situ X-ray Diffraction Study of Na ⁺ Saturated Montmorillonite Exposed to Variably Wet Super Critical CO ₂ Ilton, Eugene S.; Schaef, H. Todd; Qafoku, Odeta Environmental Science & Technology, Vol. 46, Issue 7 https://doi.org/10.1021/es300234v	journal	March 2012
The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs Ross, Daniel J. K.; Marc Bustin, R. Marine and Petroleum Geology, Vol. 26, Issue 6 https://doi.org/10.1016/j.marpetgeo.2008.06.004	journal	June 2009
A simple method for partial purification of reference clays Arroyo, L. Jacqueline; Li, Hui; Teppen, Brian J. clays and clay minerals, Vol. 53, Issue 5 https://doi.org/10.1346/CCMN.2005.0530507	journal	October 2005
Hydrophobic Solvation of Gases (CO ₂ , CH ₄ , H ₂ , Noble Gases) in Clay Interlayer Nanopores Gadikota, Greeshma; Dazas, Baptiste; Rother, Gernot The Journal of Physical Chemistry C, Vol. 121, Issue 47 https://doi.org/10.1021/acs.jpcc.7b09768	journal	November 2017
An investigation into the thermodynamic characteristics of methane adsorption on different clay minerals Liang, Lixi; Xiong, Jian; Liu, Xiangjun Journal of Natural Gas Science and Engineering, Vol. 33 https://doi.org/10.1016/j.jngse.2016.06.024	journal	July 2016
Molecular Dynamics Study of CO ₂ and H ₂ O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite Loganathan, Narasimhan; Yazaydin, A. Ozgur; Bowers, Geoffrey M. The Journal of Physical Chemistry C, Vol. 121, Issue 44 https://doi.org/10.1021/acs.jpcc.7b06825	journal	October 2017
Infrared spectra of methane adsorbed by ion-exchanged ZSM-5 zeolites Yamazaki, Tatsuya; Watanuki, Isao; Ozawa, Sentaro Langmuir, Vol. 4, Issue 2 https://doi.org/10.1021/la00080a031	journal	March 1988
Methane Aqueous Fluids in Montmorillonite Clay Interlayer under Near-Surface Geological Conditions: A Grand Canonical Monte Carlo and Molecular Dynamics Simulation Study Rao, Qi; Leng, Yongsheng The Journal of Physical Chemistry B, Vol. 118, Issue 37 https://doi.org/10.1021/jp507884w	journal	September 2014
The Environmental Costs and Benefits of Fracking Jackson, Robert B.; Vengosh, Avner; Carey, J. William Annual Review of Environment and Resources, Vol. 39, Issue 1 https://doi.org/10.1146/annurev-environ-031113-144051	journal	October 2014
Shale Gas and Hydrofracturing Schnoor, Jerald L. Environmental Science & Technology, Vol. 46, Issue 9 https://doi.org/10.1021/es3011767	journal	April 2012
In Situ Molecular Spectroscopic Evidence for CO ₂ Intercalation into Montmorillonite in Supercritical Carbon Dioxide Loring, John S.; Schaef, Herbert T.; Turcu, Romulus V. F. Langmuir, Vol. 28, Issue 18 https://doi.org/10.1021/la301136w	journal	April 2012
Competitive sorption of CO2 and H2O in 2:1 layer phyllosilicates Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki-Alexandra Geochimica et Cosmochimica Acta, Vol. 161 https://doi.org/10.1016/j.gca.2015.03.027	journal	July 2015
Role of Cations in CO ₂ Adsorption, Dynamics, and Hydration in Smectite Clays under in Situ Supercritical CO ₂ Conditions Bowers, Geoffrey M.; Schaef, H. Todd; Loring, John S. The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b11542	journal	December 2016
Effect of Interlayer Ions on Methane Hydrate Formation in Clay Sediments Yeon, Sun-Hwa; Seol, Jiwoong; Seo, Young-ju The Journal of Physical Chemistry B, Vol. 113, Issue 5 https://doi.org/10.1021/jp810079c	journal	January 2009
Interpretation of carbon-13 NMR of methane/propane hydrates in the metastable/nonequilibrium region Fleyfel, F.; Song, K. Y.; Kook, A. The Journal of Physical Chemistry, Vol. 97, Issue 25 https://doi.org/10.1021/j100127a024	journal	June 1993
Water Solubility at Saturation for CO ₂ –CH ₄ Mixtures at 323.2 K and 9.000 MPa Loring, John S.; Bacon, Diana H.; Springer, Ronald D. Journal of Chemical & Engineering Data, Vol. 62, Issue 5 https://doi.org/10.1021/acs.jced.6b00999	journal	April 2017
Formation and Restacking of Disordered Smectite Osmotic Hydrates Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M. Clays and Clay Minerals, Vol. 63, Issue 6 https://doi.org/10.1346/CCMN.2015.0630602	journal	December 2015
H ₂ O and Cation Structure and Dynamics in Expandable Clays: ² H and ³⁹ K NMR Investigations of Hectorite Bowers, Geoffrey M.; Bish, David L.; Kirkpatrick, R. James The Journal of Physical Chemistry C, Vol. 112, Issue 16 https://doi.org/10.1021/jp7119087	journal	March 2008
A General Correlation for the ¹²⁹ Xe NMR Chemical Shift−Pore Size Relationship in Porous Silica-Based Materials Terskikh, Victor V.; Moudrakovski, Igor L.; Breeze, Steven R. Langmuir, Vol. 18, Issue 15 https://doi.org/10.1021/la025714x	journal	July 2002
Potential Restrictions for CO ₂ Sequestration Sites Due to Shale and Tight Gas Production Elliot, T. R.; Celia, M. A. Environmental Science & Technology, Vol. 46, Issue 7 https://doi.org/10.1021/es2040015	journal	March 2012
Molecular Level Investigation of CH ₄ and CO ₂ Adsorption in Hydrated Calcium–Montmorillonite Lee, Mal-Soon; McGrail, B. Peter; Rousseau, Roger The Journal of Physical Chemistry C, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcc.7b05364	journal	November 2017

Cited By (1)

Understanding methane/carbon dioxide partitioning in clay nano- and meso-pores with constant reservoir composition molecular dynamics modeling Loganathan, Narasimhan; Bowers, Geoffrey M.; Ngouana Wakou, Brice F. Physical Chemistry Chemical Physics, Vol. 21, Issue 13 https://doi.org/10.1039/c9cp00851a	journal	January 2019

Similar Records

Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

Journal Article · Sun May 06 20:00:00 EDT 2018 · ACS Earth and Space Chemistry · OSTI ID:1543713

Influence of Smectite Structure and Hydration on Supercritical Methane Binding and Dynamics in Smectite Pores

Journal Article · Wed Dec 04 23:00:00 EST 2019 · Journal of Physical Chemistry C · OSTI ID:1578012

Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

Citation Formats

References (54)

Cited By (1)

Similar Records

Related Subjects