Ion Valency and Concentration Effect on the Structural and Thermodynamic Properties of Brine-Decane Interfaces with...

Salt ion valency and concentration vary in actual oil reservoirs, which play an important role in the functionalities of surfactant formula during chemical flooding processes to enhance oil recovery. Herein, we report a molecular dynamics (MD) study to investigate the ion valency and concentration effect on the structural and thermodynamic properties of brine-decane interfaces with anionic surfactant (SDS), under typical reservoir conditions (353 K and 200 bar). We use two different cations (Na⁺ and Ca²⁺) and a wide range of ion concentrations (up to 3.96 M) to simulate reservoir conditions. We find that ion valency has a significant effect on the molecular configurations, which further influences the thermodynamic properties. Ca²⁺ ions can have a strong adsorption at the interface due to the strong electrostatic interactions between Ca²⁺ ions and SDS, which also results in the Cl^- ion enrichment at the interface. Furthermore, Ca²⁺ ions can form pentagon-like SDS-Ca²⁺ complexes through SDS-Ca²⁺-SDS cation bridging, which renders a nonuniform distribution of SDS at the interface. On the other hand, the cation bridging density monotonically increases as ion concentration increases for the systems without Ca²⁺ ions, while first increases, then decreases for the systems with Ca²⁺ ions. This is because the accumulation of Cl^- ions at the interface at high salt concentrations can melt SDS-Ca²⁺ complexes. This work should provide new insights into the structural and thermodynamic properties of brine-oil interfaces with an anionic surfactant, which can facilitate the optimization of chemical flooding processes.