Wettability of Calcite Surfaces: Impacts of Brine Ionic Composition and Oil Phase Polarity at Elevated Temperature and Pressure Conditions.

Abstract

The interactions among the polar components of oil, aqueous phase ions, and carbonate minerals, as well as their subsequent effects on surface wettability, can significantly impact the fluid distribution and recovery in a hydrocarbon reservoir. In this study, we investigate the adsorption/desorption of molecules from oils with different levels of polarity on calcite surfaces during different displacement processes under elevated pressure and temperature conditions. We measured dynamic contact angles (CA) on untreated and aged calcite substrates using brines with different salinities and compositions and model oils, that is, mixtures of varying concentrations of stearic acid (SA) and n-decane. In particular, the impacts of the concentrations of Ca2+, SO42-, and OH- ions on the adsorption phenomena were explored. For the nonpolar oil, increasing brine salinity or removing Ca2+ ions from the aqueous phase impacted the potentials of oil-brine and brine-mineral interfaces and shifted the wettability of calcite surface toward more water-wet conditions. In the presence of polar oil, the adsorption of the polar components controls the surface wettability. Higher concentrations of Ca2+/SO42- could facilitate/obstruct the polar component adsorption and thus increase/decrease the dynamic oil-water CAs. It is also observed that the brine salinity does not impact the wettability if excess SA is added to the oil phase, that is, if the oil phase is strongly polar. Moreover, the adsorption of SA on the calcite surface under experimental conditions is found to be reversible during the displacement events. The surface energy calculation for the adsorption process indicates that the surface coverage of calcite by SA is more sensitive to the presence of Ca2+ in brine than the concentration of polar components in oil. We also conducted several experiments on calcite substrates aged with SA. The measurements demonstrate that the adsorbed SA molecules are detached when the aged mineral surface is exposed to a lower-salinity brine at high temperatures, and the SA molecules could be adsorbed back on the surface once the displacement is halted.