The low-salinity effect (LSE) in carbonate rock has been less explored in comparison to sandstone rock. Laboratory experiments have shown that brine composition and (somewhat reduced) salinity can have a positive impact on oil recovery in carbonates. However, the mechanism leading to improved oil recovery in carbonate rock is not well understood. Several studies showed that a positive low-salinity flooding (LSF) effect might be associated with dissolution of rock; however, because of equilibration, dissolution may not contribute at reservoir scale, which would make LSF for carbonate rock less attractive for field applications. This raises now the question whether calcite dissolution is the primary mechanism of the LSF effect. In this paper, we aim to first demonstrate the positive response of carbonate rock to low salinity and then to gain insight into the underlying mechanism(s) specific to carbonate rock. We followed a similar methodology as in sandstone rock [Kinetics of low-salinity-flooding effect Mahani H. Berg S. Ilic D. Bartels W.-B. Joekar-Niasar V. Mahani H. Berg S. Ilic D. Bartels W.-B. Joekar-Niasar V. SPE J.201520820, DOI: 10.1021/ef5023847] using a model system comprised of carbonate surfaces obtained from crushed carbonate rocks. Wettability alteration upon exposure to low-salinity brine was examined by continuous monitoring of the contact angle. Furthermore, the effective surface charge at oil–water and water–rock interfaces was quantified via ζ-potential measurements. Mineral dissolution was addressed both experimentally and with geochemical modeling using PHREEQC. Two carbonate rocks with different mineralogy were investigated: limestone and Silurian dolomite. Four types of brines were used: high-salinity formation water (FW), seawater (SW), 25× diluted seawater (25dSW), and 25× diluted seawater equilibrated with calcite (25dSWEQ). It was observed that, by switching from FW to SW, 25dSW, and 25dSWEQ, the limestone surface became less oil-wet. The results with SW and 25dSWEQ suggest that the LSE occurs even in the absence of mineral dissolution, because no dissolution is expected in SW and none in 25dSWEQ. The wettability alteration to a less oil-wetting state by low salinity is consistent with the ζ-potential data of limestone, indicating that, at lower salinities, the charges at the limestone–brine interface become more negative, indicative of a weaker electrostatic adhesion between the oil–brine and rock–brine interfaces, thus recession of the three-phase contact line. In comparison to limestone, a smaller contact angle reduction was observed with dolomite. This is again consistent with the ζ-potential of dolomite, generally showing more positive charges at higher salinities and less decrease at lower salinities. This implies that oil detachment from the dolomite surface requires a larger reduction of adhesion forces at the contact line than limestone. Our study concludes that surface charge change is likely to be the primary mechanism, which means that there is a positive LSE in carb...

Summary Laboratory studies have shown that wettability of carbonate rock can be altered to a less-oil-wetting state by manipulation of brine composition and reduction of salinity. Our recent study (Mahani et al. 2015b) suggests that surface-charge alteration is likely to be the driving mechanism of the low-salinity effect in carbonates. Various studies have already established the sensitivity of carbonate-surface charge to brine salinity, pH value, and potential-determining ions in brines. However, in the majority of the studies, single-salt brines or model-carbonate rocks have been used and it is fairly unclear how natural rock reacts to reservoir-relevant brine as well as successive brine dilution; whether different types of carbonate-reservoir rocks exhibit different electrokinetic properties; and how the surface-charge behavior obtained at different brine salinities and pH values can be explained. This paper presents a comparative study aimed at gaining more insight into the electrokinetics of different types of carbonate rock. This is achieved by ζ-potential measurements on Iceland spar calcite and three reservoir-related rocks—Middle Eastern limestone, Stevns Klint chalk, and Silurian dolomite outcrop—over a wide range of salinity, brine composition, and pH values. With a view to arriving at a more-tractable approach, a surface-complexation model (SCM) implemented in PHREEQC software (Parkhurst and Appelo 2013) is developed to relate our understanding of the surface reactions to measured ζ-potentials. It was found that regardless of the rock type, the trends of ζ-potentials with salinity and pH are quite similar. For all cases, the surface charge was found to be positive in high-salinity formation water (FW), which should favor oil-wetting. The ζ-potential successively decreased toward negative values when the brine salinity was lowered to seawater (SW) level and diluted SW. At all salinities, the ζ-potential showed a strong dependence on pH, with positive slope that remained so even with excessive dilution. The sensitivity of the ζ-potential to pH change was often higher at lower salinities. The existing SCMs cannot predict the observed increase of ζ-potential with pH; therefore, a new model is proposed to capture this feature. According to modeling results, formation of surface species, particularly >CaSO4− and to a lower extent >CO3Ca+ and >CO3Mg+, strongly influence the total surface charge. Increasing the pH turns the negatively charged moiety >CaSO4− into both negatively charged >CaCO3− and neutral > CaOH entities. (Note that throughout this paper, the symbol > indicates surface complexes.) This substitution reduces the negative charge of the surface. The surface concentration of >CO3Ca+ and >CO3Mg+ moieties changes little with change of pH. Nevertheless, besides similarities in ζ-potential trends, there exist notable differences in terms of magnitude and the isoelectric point (IEP), even between carbonates that are mainly composed of calcite. Among all the samples, chalk particles exhibited the most negative surface charges, followed by limestone. In contrast to this, dolomite particles showed the most positive ζ-potential, followed by calcite crystal. Overall, chalk particles exhibited the highest surface reactivity to pH and salinity change, whereas dolomite particles showed the lowest.

Summary Low-salinity waterflooding (LSF) is one of the least-understood enhanced-oil-recovery (EOR)/improved-oil-recovery (IOR) methods, and proper understanding of the mechanism(s) leading to oil recovery in this process is needed. However, the intrinsic complexity of the process makes fundamental understanding of the underlying mechanism(s) and the interpretation of laboratory experiments difficult. Therefore, we use a model system for sandstone rock of reduced complexity that consists of clay minerals (Na-montmorillonite) deposited on a glass substrate and covered with crude-oil droplets and in which different effects can be separated to increase our fundamental understanding. We focus particularly on the kinetics of oil detachment when exposed to low-salinity (LS) brine. The system is equilibrated first under high-salinity (HS) brine and then exposed to brines of varying (lower) salinity while the shape of the oil droplets is continuously monitored at high resolution, allowing for a detailed analysis of the contact angle and the contact area as a function of time. It is observed that the contact angle and contact area of oil with the substrate reach a stable equilibrium at HS brine and show a clear response to the LS brine toward less-oil-wetting conditions and ultimately detachment from the clay substrate. This behavior is characterized by the motion of the three-phase (oil/water/solid) contact line that is initially pinned by clay particles at HS conditions, and pinning decreases upon exposure to LS brine. This leads to a decrease in contact area and contact angle that indicates wettability alteration toward a more-water-wet state. When the contact angle reaches a critical value at approximately 40 to 50°, oil starts to detach from the clay. During detachment, most of the oil is released, but in some cases a small amount of oil residue is left behind on the clay substrate. Our results for different salinity levels indicate that the kinetics of this wettability change correlates with a simple buoyancy- over adhesion-force balance and has a time constant of hours to days (i.e., it takes longer than commonly assumed). The unexpectedly long time constant, longer than expected by diffusion alone, is compatible with an electrokinetic ion-transport model (Nernst-Planck equation) in the thin water film between oil and clay. Alternatively, one could explain the observations only by more-specific [non- Derjaguin–Landau–Verwey–Overbeek (DLVO) type] interactions between oil and clay such as cation-bridging, direct chemical bonds, or acid/base effects that tend to pin the contact line. The findings provide new insights into the (sub) pore-scale mechanism of LSF, and one can use them as the basis for upscaling to, for example, pore-network scale and higher scales (e.g., core scale) to assess the impact of the slow kinetics on the time scale of an LSF response on macroscopic scales.

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It has been proposed that increased oil recovery in carbonates by modification of ionic composition or altering salinity occurs mainly at a temperature exceeding 70–80 °C. The argument was that elevated temperatures enhance adsorption of the potential determining ions which then modifies wettability to a less-oil-wetting state. According to this rationale, it becomes questionable if diluted brines or brines without these ions can be still applicable. Therefore, the aim of this paper is to investigate if the wettability alteration truly depends on temperature and if so how the trend with temperature can be explained. We followed a combined experimental and theoretical modeling approach. The effect of brine composition and temperature on carbonate wettability was probed by monitoring contact angle change of sessile oil droplets upon switching from high salinity to lower salinity brines. IFT measurements as a function of salinity and temperature along with extensive ζ-potential measurements as a function of salinity, pH, temperature, and rock type were conducted. Interaction potentials between oil and carbonate surfaces were estimated based on DLVO theory, and its consistency with oil-droplet data was checked to draw conclusions on plausible mechanisms. Three carbonate rocks (two limestones and one dolomite) were used along with two reservoir crude oils, high salinity formation water (FW), seawater (SW), and 25 times diluted seawater (25dSW) as low salinity (LS) brine. It was observed that (i) wettability alteration to a less-oil-wetting state can occur at ambient temperature for specific rock types and brines, and (ii) there is no univocal increase in response to SW and LS brine at elevated temperature. The largest improvement in wettability was observed for dolomite, while, among the limestones, only one rock type showed noticeable wettability improvement at elevated temperature with SW. The difference in behavior between limestones and dolomite indicates that the response to brine composition change depends on rock type and mineralogy of the sample. These observations are consistent with the ζ-potential trends with salinity at a given temperature. Dolomite generally shows more positive ζ-potential than limestones. However, even the two limestones react differently to lowering salinity and exhibit different magnitude of ζ-potential. Moreover, it is observed that, at a specific salinity, an increase in temperature leads to reduction of ζ-potential magnitude on both rock/brine and oil/brine interfaces toward zero potential. This can affect positively or negatively the degree of wettability alteration (to a less-oil-wetting state) at elevated temperature depending on the sign of oil/brine and rock/brine ζ-potential in SW/LS. The observed trends are reflected in the DLVO calculations which show consistency with contact angle trends with temperature and salinity. According to the DLVO calculation, the lack of response to SW/LS in some of the systems above can be explained by stronger electrostatic attractive forces und...