Ionic Interactions at the Crude Oil–Brine–Rock Interfaces Using Different Surface Complexation Models and DLVO Theory: Application to Carbonate Wettability

Abstract

The impact of ionic association with the carbonate surface and its influence toward carbonate wettability remains unclear and is an important topic of interest in the current literature. In this work, a triple layer model (TLM) approach was used to capture the electrokinetic interactions at both calcite–brine and oil–brine interfaces. The developed TLM was assembled against measured ζ-potential values from the literature, successfully capturing the trends and closely matching the ζ-potential magnitudes. The developed TLM was compared to a diffused layer model (DLM) presented in previous works, with the DLM showing a better match to the ζ-potential values for seawater brine solutions. The ζ-potential values predicted from both surface complexation models (SCMs) were used to calculate the total interaction energy (or potential) based on the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory. It was observed that low Mg2+ and high SO42– concentrations in modified composition brine (MCB) made the calcite–brine interface more negative. However, at the oil–brine interface, low Mg2+ made the oil–brine interface more negative but high SO42– concentrations slightly shifted the oil–brine ζ-potential toward negative. At the crude oil–brine–rock (COBR) interfaces, low Mg2+ and high SO42– concentrations in the MCB were observed to generate a greater repulsive interaction energy, which could trigger carbonate wettability alteration toward water wetness. The absolute sum of the ζ-potential at both interfaces was observed to be correlated to the total interaction potential at a 0.25 nm separating distance. Thus, an increase in the absolute sum of the ζ-potentials would generate a greater repulsive interaction potential and trigger wettability alteration. Therefore, these SCMs can be applied to design modified composition brine capable of triggering a repulsive interaction energy to alter carbonate wettability toward water wetness.