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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.

We present Monte Carlo simulations of nonionic surfactant adsorption at the liquid/vapor interface of a monatomic solvent. All molecules in the system, solvent and surfactant, are characterized by the Lennard-Jones (LJ) potential using differing interaction parameters. Surfactant molecules consist of an amphiphilic chain with a solvophilic head and a solvophobic tail. Adjacent atoms along the surfactant chain are connected by finitely extensible harmonic springs. Solvent molecules move via the Metropolis random-walk algorithm, whereas surfactant molecules move according to the continuum configurational bias Monte Carlo (CBMC) method. We generate quantitative thermodynamic adsorption and surface tension isotherms in addition to surfactant radius of gyration, tilt angles, and potentials of mean force. Surface tension simulations compared to those calculated from the simulated adsorbed amounts and the Gibbs adsorption isotherm agree confirming equilibrium in our simulations. We find that the classical Langmuir isotherm is obeyed for our LJ surfactants over the range of head and tail lengths studied. Although simulated surfactant chains in the bulk solution exhibit random orientations, surfactant chains at the interface orient roughly perpendicular and the tails elongate compared to bulk chains even in the submonolayer adsorption regime. At a critical surfactant concentration, designated as the critical aggregation concentration (CAC), we find aggregates in the solution away from the interface. At higher concentrations, simulated surface tensions remain practically constant. Using the simulated potential of mean force in the submonolayer regime and an estimate of the surfactant footprint at the CAC, we predict a priori the Langmuir adsorption constant, KL, and the maximum monolayer adsorption, Gammam. Adsorption is driven not by proclivity of the surfactant for the interface, but by the dislike of the surfactant tails for the solvent, that is by a "solvophobic" effect. Accordingly, we establish that a coarse-grained LJ surfactant system mimics well the expected equilibrium behavior of aqueous nonionic surfactants adsorbing at the air/water interface.

A novel recycle reactor has been designed to determine the interfacial activity of hydroxynitrile lyase in a diisopropyl ether (DIPE)/water two-phase system. The reactor provides a known interfacial area. Enzyme activity toward mandelonitrile cleavage is continuously measured in the reactor by following benzaldehyde product formation in the DIPE organic phase with an optical flow cell. For the first time, we establish that this enzymatic reaction is carried out by the hydroxynitrile lyase residing at the organic solvent/water interface and not in the aqueous bulk phase. Hydroxynitrile lyase adsorbs at the interface and exhibits extraordinary stability. Denaturation does not occur over several hours, although the surface pressure increases under the same conditions over this time span. Increases in surface pressure indicate enzyme penetration through the interface although no loss of enzyme activity is observed. Adsorption of p-Hnl at the interface is fit by the Langmuir equilibrium adsorption model with an adsorption equilibrium constant of 0.032 L mg(-1). For the mandelonitrile-cleavage reaction at ambient temperature, p-Hnl follows Michaelis-Menten kinetics at the interface with a Michaelis constant of 14.4 mM and a specific activity close that for the bulk aqueous phase.