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

Abstract

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 themore » 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.« less

Authors:

Greathouse, J. A.  ^[1];

• Search DOE PAGES for author "Greathouse, J. A."
• Search DOE PAGES for ORCID "0000-0002-4247-3362"

Cygan, R. T.  ^[1];

• Search DOE PAGES for author "Cygan, R. T."
• Search DOE PAGES for ORCID "0000-0003-1262-6177"

Fredrich, J. T. ^[2]; Jerauld, G. R. ^[2]

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+ Show Author Affiliations

1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
2. BP America, Houston, TX (United States)

Publication Date:

Thu Sep 28 00:00:00 EDT 2017

Research Org.:

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:

USDOE National Nuclear Security Administration (NNSA); Work for Others (WFO); BP America

OSTI Identifier:

1398786

Report Number(s):

SAND-2017-10428J
Journal ID: ISSN 1932-7447; 657315

Grant/Contract Number:  

AC04-94AL85000; NA0003525

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Physical Chemistry. C

Additional Journal Information:

Journal Volume: 121; Journal Issue: 41; Journal ID: ISSN 1932-7447

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

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