skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Adsorption of Aqueous Crude Oil Components on the Basal Surfaces of Clay Minerals: Molecular Simulations Including Salinity and Temperature Effects

Journal Article · · Journal of Physical Chemistry. C
ORCiD logo [1]; ORCiD logo [1];  [2];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. BP America, Houston, TX (United States)
+ Show Author Affiliations

Molecular simulations of the adsorption of representative organic molecules onto the basal surfaces of various clay minerals were used to assess the mechanisms of enhanced oil recovery associated with salinity changes and water flooding. Simulations at the density functional theory (DFT) and classical levels provide insights into the molecular structure, binding energy, and interfacial behavior of saturate, aromatic, and resin molecules near clay mineral surfaces. Periodic DFT calculations reveal binding geometries and ion pairing mechanisms at mineral surfaces while also providing a basis for validating the classical force field approach. Through classical molecular dynamics simulations, the influence of aqueous cations at the interface and the role of water solvation are examined to better evaluate the dynamical nature of cation-organic complexes and their co-adsorption onto the clay surfaces. The extent of adsorption is controlled by the hydrophilic nature and layer charge of the clay mineral. All organic species studied showed preferential adsorption on hydrophobic mineral surfaces. However, the anionic form of the resin (decahydro-2-naphthoic acid)—expected to be prevalent at near-neutral pH conditions in petroleum reservoirs—readily adsorbs to the hydrophilic kaolinite surface through a combination of cation pairing and hydrogen bonding with surface hydroxyl groups. Analysis of cation-organic pairing in both the adsorbed and desorbed states reveals a strong preference for organic anions to coordinate with divalent calcium ions rather than monovalent sodium ions, lending support to current theories regarding low-salinity water flooding.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); Work for Others (WFO); BP America
Grant/Contract Number:
AC04-94AL85000; NA0003525
OSTI ID:
1398786
Report Number(s):
SAND-2017-10428J; 657315
Journal Information:
Journal of Physical Chemistry. C, Vol. 121, Issue 41; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 48 works
Citation information provided by
Web of Science

References (46)

Influence of brine composition and fines migration on crude oil/brine/rock interactions and oil recovery journal December 1999
Modeling Low-Salinity Waterflooding journal December 2008
Molecular Dynamic Simulations of Montmorillonite–Organic Interactions under Varying Salinity: An Insight into Enhanced Oil Recovery journal March 2015
Modeling Acid Oil Component Interactions with Carbonate Reservoirs: A First-Principles View on Low Salinity Recovery Mechanisms journal August 2014
Molecular Dynamics Studies of Fluid/Oil Interfaces for Improved Oil Recovery Processes journal December 2012
Adsorption mechanism of oil components on water-wet mineral surface: A molecular dynamics simulation study journal September 2013
An ab Initio and Classical Molecular Dynamics Investigation of the Structural and Vibrational Properties of Talc and Pyrophyllite journal August 2007
Structure and energetics of ligand binding to proteins:Escherichia coli dihydrofolate reductase-trimethoprim, a drug-receptor system journal January 1988
Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field journal January 2004
Molecular Controls on Kaolinite Surface Charge journal November 1996
Water and ions in clays: Unraveling the interlayer/micropore exchange using molecular dynamics journal November 2007
Up-Scaling of Molecular Diffusion Coefficients in Clays: A Two-Step Approach journal March 2011
Elucidating the Crystal Face- and Hydration-Dependent Catalytic Activity of Hydrotalcites in Biodiesel Production journal December 2010
Thermodynamically Consistent Force Fields for the Assembly of Inorganic, Organic, and Biological Nanostructures: The INTERFACE Force Field journal January 2013
Toward Modeling Clay Mineral Nanoparticles: The Edge Surfaces of Pyrophyllite and Their Interaction with Water journal November 2014
Vibrational Analysis of Brucite Surfaces and the Development of an Improved Force Field for Molecular Simulation of Interfaces journal April 2014
Effects of thermodynamic ensembles and mineral surfaces on interfacial water structure journal January 2012
Anaerobic hydrocarbon biodegradation in deep subsurface oil reservoirs journal September 2004
An all‐electron numerical method for solving the local density functional for polyatomic molecules journal January 1990
From molecules to solids with the DMol3 approach journal November 2000
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
Rietveld Refinement of the Kaolinite Structure at 1.5 K journal January 1993
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
Molecular dynamics simulation of uranyl(vi) adsorption equilibria onto an external montmorillonite surface journal January 2005
Water Structure and Aqueous Uranyl(VI) Adsorption Equilibria onto External Surfaces of Beidellite, Montmorillonite, and Pyrophyllite:  Results from Molecular Simulations journal June 2006
Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite journal February 2014
Implementation of a Morse potential to model hydroxyl behavior in phyllosilicates journal April 2009
Swelling Properties of Montmorillonite and Beidellite Clay Minerals from Molecular Simulation: Comparison of Temperature, Interlayer Cation, and Charge Location Effects journal August 2015
Molecular Dynamics Simulations of Structural and Mechanical Properties of Muscovite: Pressure and Temperature Effects
  • Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 28 https://doi.org/10.1021/jp303143s
journal July 2012
Nanoconfined Water in Magnesium-Rich 2:1 Phyllosilicates journal June 2009
Structure, Energetics, and Dynamics of Smectite Clay Interlayer Hydration: Molecular Dynamics and Metadynamics Investigation of Na-Hectorite journal March 2013
A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions journal September 2006
Hydration Properties and Interlayer Organization of Water and Ions in Synthetic Na-Smectite with Tetrahedral Layer Charge. Part 2. Toward a Precise Coupling between Molecular Simulations and Diffraction Data journal December 2010
Water Dynamics in Hectorite Clays: Infuence of Temperature Studied by Coupling Neutron Spin Echo and Molecular Dynamics journal April 2011
Microscopic Simulations of Interlayer Structure and Dynamics in Bihydrated Heteroionic Montmorillonites journal February 2003
Molecular Simulation of Structure and Diffusion at Smectite–Water Interfaces: Using Expanded Clay Interlayers as Model Nanopores journal July 2015
Alcohol and Thiol Adsorption on (Oxy)hydroxide and Carbon Surfaces: Molecular Dynamics Simulation and Desorption Experiments journal December 2012
Mobility of Na and Cs on Montmorillonite Surface under Partially Saturated Conditions journal August 2013
Resolving diffusion in clay minerals at different time scales: Combination of experimental and modeling approaches journal July 2014
A molecular dynamics simulation of a water model with intramolecular degrees of freedom journal January 1987
Computer simulations of NaCl association in polarizable water journal March 1994
Solvent Structure, Dynamics, and Ion Mobility in Aqueous Solutions at 25 °C journal May 1998
Intercalation of Ethylene Glycol in Smectites: Several Molecular Simulation Models Verified by X-ray Diffraction Data journal August 2016
Methylene Blue Adsorption on the Basal Surfaces of Kaolinite: Structure and Thermodynamics from Quantum and Classical Molecular Simulation journal June 2015
Assessment of ten DFT methods in predicting structures of sheet silicates: Importance of dispersion corrections journal September 2012
Wettability Alteration of Clay in Solid-Stabilized Emulsions journal June 2011

Cited By (2)

Wetting Behavior of Tight Rocks: From Core Scale to Pore Scale journal November 2018
Effect of confinement on the adsorption behavior of inorganic and organic ions at aqueous–cyclohexane interfaces: a molecular dynamics study journal January 2019

Similar Records

Molecular Dynamics Simulation of Resin Adsorption at Kaolinite Edge Sites: Effect of Surface Deprotonation on Interfacial Structure
Journal Article · Thu Oct 05 00:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1398786
+2 more
A novel, integrated treatment system for coal waste waters. Quarterly report, March 2, 1993--June 1, 1993
Technical Report · Wed Sep 01 00:00:00 EDT 1993 · OSTI ID:1398786
Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions
Journal Article · Wed Jun 14 00:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1398786
+1 more

Related Subjects

54 ENVIRONMENTAL SCIENCES
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY