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Modified or low-salinity waterflooding of carbonate oil reservoirs is of considerable economic interest because of potentially inexpensive incremental oil production. The injected modified brine changes the surface chemistry of the carbonate rock and crude oil interfaces and detaches some of adhered crude oil. Composition design of brine modified to enhance oil recovery is determined by labor-intensive trial-and-error laboratory corefloods. Unfortunately, limestone, which predominantly consists of aqueous-reactive calcium carbonate, alters injected brine composition by mineral dissolution/precipitation. Accordingly, the rock reactivity hinders rational design of brines tailored to improve oil recovery. Previously, we presented a theoretical analysis of 1D, single-phase brine injection into calcium carbonate-rock that accounts for mineral dissolution, ion exchange, and dispersion (Yutkin et al. in SPE J 23(01):084–101, 2018. 10.2118/182829-PA). Here, we present the results of single-phase waterflood-brine experiments that verify the theoretical framework. We show that concentration histories eluted from Indiana limestone cores possess features characteristic of fast calcium carbonate dissolution, 2:1 ion exchange, and high dispersion. The injected brine reaches chemical equilibrium inside the porous rock even at injection rates higher than 3.5 $$\times$$ × 10$$^{-3}$$ - 3 m s$$^{-1}$$ - 1 (1000 ft/day). Ion exchange results in salinity waves observed experimentally, while high dispersion is responsible for long concentration history tails. Using the verified theoretical framework, we briefly explore how these processes modify aqueous-phase composition during the injection of designer brines into a calcium-carbonate reservoir. Because of high salinity of the initial and injected brines, ion exchange affects injected concentrations only in high surface area carbonates/limestones, such as chalks. Calcium-carbonate dissolution only affects aqueous solution pH. The rock surface composition is affected by all processes.

This work focuses on a potentially economic incremental oil-recovery process, where a brine amended with inexpensive salts (in contrast to expensive surfactants and other chemicals) is injected into a reservoir to increase oil production. Historically, this process received the name of low salinity waterflooding (LSW) although the salinity is not always low(er). Nevertheless, we keep using this terminology for historical reasons.The idea of LSW has been known for three decades, but to the best of our knowledge no specific brine recipes that guarantee success have been presented so far. The reasons hide in the problem's complexity, disagreements in the scientific community, and a race to publish rather than to understand the fundamental principles behind the process.In this paper, we present an experimental model system that captures many of the important fundamental features of the natural process of crude oil attachment to mineral surfaces, but at the same time decomposes this complex process into simpler parts that can be more precisely controlled and understood. We systematically investigate the first-order chemical interactions contributing to the well-known strong attachment of crude oil to minerals using SiO2 as a mineral for its surface chemistry simplicity.Our preliminary results suggest that magnesium and sulfate ions are potent in detaching amino/ammonium-based linkages of crude oil with a SiO2 surface. However, when used together in the form of MgSO4, they lose part of their activity to the formation of a MgSO4 ion pairs. We also find that sulfate-detachment propensity stems not from the interaction with prototype mineral surface, but rather from the interactions with the crude oil-brine interface analog. We continue the systematic study of the ion effects on crude oil detachment, with and more results following in the future.