Carbonate mineral effect on surface charge change during low-salinity imbibition

Low-salinity waterflooding is a relatively simple and cheap improved oil recovery technique in which the reservoir salinity is optimized to increase oil recovery. Multivalent ion enriched as well as diluted brines have shown promising potential to increase oil production over conventional waterflooding. While the literature generally acknowledges that low-salinity improves oil recovery, the physical mechanisms behind low-salinity effects are still controversial. Surface charge change refers to a low-salinity mechanism in which modified brine is believed to cause a re-equilibrium of the carbonate surface potential. As a result of surface charge change, the rock wettability alters towards a more water-wetting state. This experimental study combines zeta potential, spontaneous imbibition, and contact angle measurements to highlight the effect of carbonate minerals on surface charge change. Initially, zeta potential measurements were conducted to compare the impact of five carbonate minerals (Indiana Limestone, Edward Limestone, Reservoir Limestone, Austin Chalk, and Silurian Dolomite) and brine compositions (Formation-water, Sea-water, and Diluted-sea-water) on carbonate surface charge. Moreover, the impact of potential determining ions (calcium, magnesium, and sulfate) on the mineral surface charge was investigated. The effect of carbonate minerals on spontaneous oil recovery was investigated by comparing the spontaneous imbibition of Formation-water, Sea-water, and Diluted-sea-water into the five carbonate minerals. Moreover, the wettability alteration during the spontaneous imbibition tests was quantified by conducting contact angle measurements. The brine-mineral zeta potential measurements were positive for Formation-water, slightly negative for Sea-water, and strongly negative for Diluted-sea-water. While calcium and magnesium ions promoted stronger positive electrical potentials, sulfate ions caused a zeta potential reduction. The magnitude of surface charge change was significantly different for the five tested carbonate minerals. Under the presence of Diluted-sea-water, the zeta potential measurements of Indiana Limestone and Austin Chalk resulted in strong negative electrical potentials. Reservoir Limestone and Edward Limestone showed less negative zeta potentials, while Silurian Dolomite and Diluted-sea-water resulted in slightly negative zeta potential results. Compared to Formation-water, Sea-water, and particularly Diluted-sea-water caused significant spontaneous oil recovery. The high spontaneous oil recovery of Diluted-sea-water and Indiana Limestone and Austin Chalk correlated with strong negative brine-mineral zeta potentials. Moderate spontaneous oil recovery was observed for the slightly negative zeta potential Sea-water and limestone/chalks systems. The contact angle measurements showed oil-wet contact angles under the presence of Formation-water, while the introduction of Sea-water and Diluted-sea-water promoted stronger water-wet contact angles. This work is one of the very few studies that investigates the effect of carbonate rock mineralogy on surface charge change and spontaneous oil recovery.