Molecular Dynamics Study on Performance of Olefin Sulfonate at the Decane–Water Interface: Effect of Molecular Architecture

Surfactant flooding has been widely employed to recover the residual oil in the oilfields. Among the various oil-displacing chemicals, olefin sulfonate isomers have been identified as effective chemical agents by many experiments due to the realization of low interfacial tension (IFT) at the oil–water interface, and tolerance for high salinity and high temperature under reservoir conditions. The molecular architecture (e.g. degree of branching) of the surfactant can significantly affect the oil–water interfacial properties and hence its performance. Herein, molecular dynamics simulations were performed to investigate the adsorption processes of alpha olefin surfactant (AOS with single-tailed structure) and internal olefin surfactant (IOS with twin-tailed structure) at the oil (n-decane) - water interface under oil reservoir condition. The results show that IOS can significantly reduce the IFT at high concentrations, and the formed monolayers at the interface are more stable compared with AOS. The steric hindrance effect by the short chain of IOS can inhibit the aggregation behavior, thus leading to larger interfacial coverage, which are favorable to separation of the water and decane phases. The larger distance between the headgroups of IOS molecules is conducive to formation of hydrogen bonds between the surfactant and water molecules, and hence enhances the interaction between the IOS and water molecules at the inerface. Based on the analysis of order parameter, the middle segment of AOS molecules and the long chain of IOS molecules are mainly contributed to the Van der Waals' interaction between the surfactant alkyl tails and decane molecules. Meanwhile, the twin-tailed structure of IOS has more favorable effective alkyl tail length (i.e. better miscibility with the oil phase) compared with the single-tailed structure of AOS. Consequently, the twin-tailed structure is superior to the single-tailed structure in terms of interfacial performance, and it is strongly suggested for the design of advanced surfactants in EOR implementation.