Electrokinetics of Carbonate/Brine Interface in Low-Salinity Waterflooding: Effect of Brine Salinity, Composition, Rock Type, and pH on ?-Potential and a Surface-Complexation Model

SPE Journal ◽  
2016 ◽  
Vol 22 (01) ◽  
pp. 53-68 ◽  
Author(s):  
Hassan Mahani ◽  
Arsene Levy Keya ◽  
Steffen Berg ◽  
Ramez Nasralla
Keyword(s):  
Surface Charge ◽  
Carbonate Rock ◽  
Rock Type ◽  
Surface Complexation ◽  
Surface Complexation Model ◽  
Ζ Potential ◽  
Low Salinity ◽  
Ph Values ◽  
Different Types ◽  
Brine Salinity

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.

Surface-Charge Alteration at the Carbonate/Brine Interface During Single-Well Chemical-Tracer Tests: Surface-Complexation Model

SPE Journal ◽  
2018 ◽  
Vol 23 (06) ◽  
pp. 2302-2315 ◽  
Author(s):  
Rasoul Khaledialidusti ◽  
Jon Kleppe
Keyword(s):  
Equilibrium State ◽  
Water Chemistry ◽  
Surface Charge ◽  
Carbonate Rock ◽  
Calcium Concentration ◽  
Surface Complexation ◽  
Calcite Dissolution ◽  
Surface Complexation Model ◽  
Chemical Tracer ◽  
Single Well

Summary Water chemistry has been shown to affect oil recovery by affecting surface charge and rock dissolution. The single-well chemical-tracer (SWCT) test is a field method to measure residual oil saturation (Sor), in which hydrolysis reaction of an ester has been known as a key process that could displace the equilibrium state of a reservoir by changing formation-water (FW) composition. Because oil mobilization during the SWCT tests causes an error in the measurement of Sor, changes in water chemistry might be a concern for the accuracy of Sor measurements. In our previous work, the extent to which different reservoir parameters might change water composition and the effect of water-chemistry changes on the calcite dissolution and the oil liberation from the carbonate-rock surfaces were extensively evaluated. In this study, the effect of water-chemistry changes on surface-charge alteration at the carbonate/brine interface has been studied by constructing and applying a surface-complexation model (SCM) that couples bulk aqueous and surface chemistry. We present how the pH drop induced by the displacement of the equilibrium state and changes in water chemistry in the formation affect surface charge in a pure-calcite carbonate rock during the SWCT tests. The results show that a pH drop during the SWCT tests while calcium concentration is held constant in the FW by ignoring calcite dissolution yields a less-positive/more-negative surface charge so that wettability of carbonate rock might be altered to a less-oil-wetting state, when the oil is negatively charged. In reality, however, calcite dissolves by water-chemistry changes during the SWCT tests, which leads to an increasing calcium concentration in the FW. Consequently, an SWCT test in carbonates is accompanied by increasing calcium concentration while pH drops, which yields an increase in the surface charge of carbonate rocks. Therefore, the pH drop does not directly affect the surface charge of carbonate rock during an SWCT test, and calcium concentration increased from calcite dissolution could control the surface charge more significantly.

Magnetite Sorption Capacity for Strontium as a Function of pH

2008 ◽  
Vol 1107 ◽  
Author(s):  
Joan de Pablo ◽  
Miquel Rovira ◽  
Javier Giménez ◽  
Ignasi Casas ◽  
Frederic Clarens
Keyword(s):  
Spent Nuclear Fuel ◽  
Surface Complexation ◽  
Retardation Factor ◽  
Alkaline Ph ◽  
Layer Model ◽  
Surface Complexation Model ◽  
Ph Values ◽  
End Products ◽  
Diffuse Layer Model ◽  
Ph Range

AbstractThe ubiquity of iron oxide minerals and their ability to retain metals on their surface can represent an important retardation factor to the mobility of radionuclides. In a deep repository for the spent nuclear fuel, the intrusion of the groundwater might produce the anoxic corrosion of the iron, with magnetite as one of the end-products. In this study, as expected considering the strontium speciation in solution, strontium is sorbed onto magnetite at alkaline pH values while at acidic pH the sorption is negligible. Magnetite is able to sorb more than the 50% of the strontium from a 8·10-6 mol·dm-3 solution at the pH range representative of most groundwater (7-9). A surface complexation model has been applied to the experimental data, allowing to explain the results using the Diffuse Layer Model (DLM) and considering the formation of the inner-sphere complex >FeOHSr2+ (with a calculated logK=2.7±0.3). Considering these data, the magnetite capacity to retain strontium and other radionuclides is discussed

Plasma modification of polyvinyltoluene and polystyrene latices

1991 ◽  
Vol 6 (4) ◽  
pp. 855-860 ◽  
Author(s):  
C.J. Zimmermann ◽  
N. Ryde ◽  
N. Kallay ◽  
R.E. Partch ◽  
E. Matijević
Keyword(s):  
Specific Surface ◽  
Surface Charge ◽  
Surface Area ◽  
Interfacial Layer ◽  
Chemical Nature ◽  
Equilibrium Constants ◽  
Surface Complexation ◽  
Surface Topology ◽  
Plasma Modification ◽  
Surface Complexation Model

Polyvinyltoluene (PVT) latex particles were etched with O2 or CF4/O2 plasma and polystyrene (PS) latex by the O2 plasma. While the effect of these treatments on the surface topology and the specific surface area was minor, the electrokinetic measurements showed a significant change in the surface charge characteristics. The interpretation of the results in terms of a surface complexation model, taking the Stern–Gouy–Chapman structure of the interfacial layer into consideration, yielded the values of the corresponding equilibrium constants, which indicated that the chemical nature and the density of the surface charged groups were altered by plasma attacks.

Comparison of a Non Electrostatic Surface Complexation Model and Surface Phase Theories for Prediction of Future Sorption Properties.

2004 ◽  
Vol 824 ◽  
Author(s):  
Allan T. Emrén ◽  
Anna-Maria Jacobsson
Keyword(s):  
Aqueous Solution ◽  
Chemical Potential ◽  
Surface Complexation ◽  
Sorption Properties ◽  
Phase Method ◽  
Detailed Knowledge ◽  
Surface Phase ◽  
Surface Complexation Model ◽  
Advantages And Disadvantages ◽  
The One

AbstractIn performance assessments, sorption of radionuclides dissolved in groundwater is mostly handled by the use of fixed Kd values. It has been well known that this approach is unsatisfying. Only during the last few years, however, tools have become available that make it possible to predict the actual Kd value in an aqueous solution that differs from the one in which the sorption properties were measured.One such approach is surface complexation (SC) that gives a detailed knowledge of the sorption properties. In SC, one tries to find what kinds of sorbed species are available on the surface and the thermodynamics for their formation from species in the bulk aqueous solution. Recently, a different approach, surface phase method (SP), has been developed. In SP, a thin layer including the surface is treated as a separate phase. In the bulk aqueous solution, the surface phase is treated as a virtual component, and from the chemical potential of this component, the sorption properties can be found.In the paper, we compare advantages and disadvantages of the two kinds of models. We also investigate the differences in predicted sorption properties of a number of radionuclides (Co, Np, Th and U). Furthermore, we discuss under which circumstances, one approach or the other is preferable.

scholarly journals Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

SPE Journal ◽  
2017 ◽  
Vol 23 (01) ◽  
pp. 84-101 ◽  
Author(s):  
Maxim P. Yutkin ◽  
Himanshu Mishra ◽  
Tadeusz W. Patzek ◽  
John Lee ◽  
Clayton J. Radke
Keyword(s):  
Ionic Strength ◽  
Ion Exchange ◽  
Crude Oil ◽  
Surface Charge ◽  
Double Layer ◽  
Carbonate Reservoir ◽  
Carbonate Reservoirs ◽  
Diffuse Double Layer ◽  
Low Salinity ◽  
Low Salinity Waterflooding

Summary Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of calcite bulk and surface equilibria draws several important inferences about the proposed LSW oil-recovery mechanisms. Diffuse double-layer expansion (DLE) is impossible for brine ionic strength greater than 0.1 molar. Because of rapid rock/brine equilibration, the dissolution mechanism for releasing adhered oil is eliminated. Also, fines mobilization and concomitant oil release cannot occur because there are few loose fines and clays in a majority of carbonates. LSW cannot be a low-interfacial-tension alkaline flood because carbonate dissolution exhausts all injected base near the wellbore and lowers pH to that set by the rock and by formation CO2. In spite of diffuse double-layer collapse in carbonate reservoirs, surface ion-exchange oil release remains feasible, but unproved.

Variable charges of a red soil from different depths: Acid-base buffer capacity and surface complexation model

2018 ◽  
Vol 159 ◽  
pp. 107-115 ◽  
Author(s):  
Ying Wang ◽  
Pengfei Cheng ◽  
Fangbai Li ◽  
Tongxu Liu ◽  
Kuan Cheng ◽  
...  
Keyword(s):  
Buffer Capacity ◽  
Surface Complexation ◽  
Red Soil ◽  
Acid Base ◽  
Surface Complexation Model ◽  
Different Depths
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