Wet Non-Aqueous Supercritical Fluid Interactions with Densified Model Rock Materials
EMSL Project ID
49782
Abstract
Our research program investigates the fundamental molecular-scale dynamics, energetics, and reactivity of geochemically relevant solid-fluid interfaces by integrating experimental spectroscopy and computational molecular modeling. These interfaces play critical roles in non-conventional gas resources, the global carbon balance, nutrient cycling, fluid transport in rock nano-pores, and pollutant transport in the lithosphere. The main objective of the research in this science-theme proposal is to study the interfaces between multi-mineral, densified materials that approximate true shale compositions and variably wet supercritical CO2, CH4, and mixtures of the two using the unique high-pressure nuclear magnetic resonance (NMR) capabilities at EMSL at conditions relevant to non-conventional gas extraction and subsurface CO2 sequestration. Our team of collaborators has a track record of linking data from EMSL's high-pressure NMR and other spectroscopic and diffraction capabilities with molecular dynamics computer modeling to understand supercritical CO2 interactions with smectite clays and smectite-organic composite materials. However, while smectites and other clay minerals make up a significant fraction of frackable and sealing shales, shales are composed of many minerals and often contain organic matter. They are also much denser with a finer scale pore structure than the individual clay samples we have been studying. Thus, the proposed work fills a knowledge gap by systematically studying how wet, non-aqueous supercritical fluids interact with densified organic, inorganic, and organic/inorganic composite materials that more closely mimic natural shales under subsurface conditions. Given our past work, we are uniquely positioned to provide detailed molecular-level insight into the effects of densification on the interactions at the solid/fluid interface. The many high-field NMR instruments and the specialized high-pressure NMR rotor system at EMSL are absolutely essential to the novel in situ scCO2 and scCH4 experiments; we cannot conduct this work anywhere else. Likewise, the densified samples need to be well-characterized, and we will take advantage of the high depth-of-field of the EMSL helium ion microscope as well. This work is a natural bridge between the Terrestrial and Subsurface Ecosystems and Molecular Transformation themes and will contribute directly to several research papers combining spectroscopic and computational results over the life of the proposal. It will also serve as the basis for a new collaborative grant proposal between several PNNL researchers and Bowers/Kirkpatrick.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2017-10-01
End Date
2019-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Bowers G.M., E.D. Walter, S.D. Burton, K.C. Schwarz, D.W. Hoyt, and R.J. Kirkpatrick. 2020. "Probing Pore Size and Connectivity in Porous Silicas Using 13C MAS NMR Spectroscopy of Supercritical Methane." Journal of Physical Chemistry C 124, no. 21:11536-11543. PNNL-SA-153506. doi:10.1021/acs.jpcc.0c02718
Bowers G.M., H.T. Schaef, Q. Miller, E.D. Walter, S.D. Burton, D.W. Hoyt, and J.A. Horner, et al. 2019. "13C NMR Spectroscopy of Methane and Carbon Dioxide in a Natural Shale." Environmental Science & Technology Letters 3, no. 3:324–328. PNNL-SA-140683. doi:10.1021/acsearthspacechem.8b00214
Bowers G.M., J.S. Loring, E.D. Walter, S.D. Burton, M.E. Bowden, D.W. Hoyt, and B.W. Arey, et al. 2019. "Influence of Smectite Structure and Hydration on Supercritical Methane Binding and Dynamics in Smectite Pores." Journal of Physical Chemistry C 123, no. 48:29231-29244. PNNL-SA-146425. doi:10.1021/acs.jpcc.9b08875
Bowers G.M., J.S. Loring, H.T. Schaef, E.D. Walter, S.D. Burton, D.W. Hoyt, and S.S. Cunniff, et al. 2018. "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." ACS Earth and Space Chemistry 2, no. 7:640-652. PNNL-SA-136218. doi:10.1021/acsearthspacechem.8b00039
Bowers G.M., J.S. Loring, H.T. Schaef, S.S. Cunniff, E.D. Walter, S.D. Burton, and R.K. Larsen, et al. 2019. "Chemical Trapping of CO2 by Clay Minerals at Reservoir Conditions: Two Mechanisms Observed by In Situ High Pressure and Temperature Experiments." ACS Earth and Space Chemistry 3, no. 6:1034-1046. PNNL-SA-140918. doi:10.1021/acsearthspacechem.9b00038
Bowers G.M., S.S. Cunniff, E.S. Ilton, H.T. Schaef, L. Kovarik, S.D. Burton, and Q. Miller, et al. 2018. "Protonation of clay in hydrated supercritical CO2." Chemistry of Materials. PNNL-SA-131616. [Unpublished]