Phase behavior of n-hexane confined in unconsolidated nanoporous media: an experimental investigation at varying pore sizes and temperatures.

We investigated the effect of confinement on the phase behavior of hexane in nanopores of mesoporous silica at varying pore diameters and temperatures using a patented gravimetric apparatus. The adsorption and desorption isotherms were experimentally measured, and the capillary condensation and evaporation pressures were calculated from the isotherms. The results show that, for all pore sizes and temperatures utilized here, the confinement of fluids significantly lowers the vapor-liquid phase transition pressures. However, its evaporation, i.e., liquid-vapor phase transition, occurs at a lower pressure than its capillary condensation counterpart. The experimental findings demonstrate that the confinement effect becomes weaker in wider nanopores due to the reduced solid-fluid interactions in larger spaces. Furthermore, it is evident from isotherms that hexane rapidly approaches a supercritical-like state at high temperatures when confined in smaller pores, resulting in an ambiguous vapor-liquid phase transition. In contrast, this behavior disappears in larger pores at similar temperatures. Moreover, the present study compares the fully gravimetric adsorption method against the thermogravimetric approach. The results show that the fully gravimetric method, which directly measures the mass of the adsorbed or condensed fluids, provides significant advantages over the thermogravimetric counterpart. The findings of this study are expected to be of fundamental interest to a wide range of science and engineering communities concerned about the behavior of heavier hydrocarbons in various industrial applications, and modeling the confined phase behavior of fluids and developing robust equations of state (EOS).

The effect of confinement on the phase behavior of propane in nanoporous media: an experimental study probing capillary condensation, evaporation, and hysteresis at varying pore sizes and temperatures.

Fundamental understanding of the phase behavior and properties of fluids under confinement is of great significance for multiple fields of engineering and science, as well as for many practical industrial applications. In particular, unconventional geological systems, such as shale reservoirs, possess nanometer-scale pores, which impose nanoconfinement on the fluid molecules. In large pores, the bulk phase behavior of fluids can be modeled by the well-established methods, such as equation of state (EOS) approaches. However, under confinement the thermodynamic properties of fluids deviate significantly from those in the bulk, thus rendering the traditional EOS methods ineffective in predicting the phase behavior of confined fluids. Recently, the PC-SAFT/Laplace EOS has been developed to better represent the fluid phase equilibria in nanopores, which incorporates a new parameter that needs to be determined from experimental data. In this study, a new dataset is presented to reflect the phase properties of propane confined within the MCM-41 pores, with the aim to improve both the general understanding of the phase behavior of hydrocarbons under confinement and to parameterize the PC-SAFT/Laplace EOS for the nanoconfined propane. For this purpose, propane adsorption and desorption isotherms are determined experimentally for a wide range of temperatures (-27 to 20 °C) in MCM-41 of three different pore sizes (nominal pore diameters of 60, 80, and 100 Å). The effects of temperature and pore diameter on the capillary condensation and evaporation pressures are discussed in detail. Furthermore, the adsorption-desorption hysteresis behavior and its progression for different pore sizes were discussed. The experimental data are modeled using the parameterized PC-SAFT/Laplace EOS, which accurately captured the effects of confinement on the capillary condensation of propane in MCM-41. In addition, this study enriches the field of nanoconfinement research by providing a new dataset exemplifying the thermodynamic characteristics of hydrocarbons in nanopores.

Synergistic Effects of Aqueous Phase Viscoelasticity and Reduced Interfacial Tension on Nonwetting Phase Displacement Efficiency: An In Situ Experimental Investigation.

This study uses in situ experimental investigation techniques to probe the synergistic effects of aqueous phase viscoelasticity and reduced interfacial tension on nonwetting phase displacement efficiency in natural porous media. Specifically, it examines the efficacy of viscoelastic surfactant (VES) solutions in enhancing oil recovery and investigates the pore-scale displacement mechanisms and VES-oil interactions. To this end, we first performed an extensive rheological characterization to select two VES solutions from multiple CTAB/NaNO3 (CTN) and Cocobetaine/SDS/NaCl (CSN) mixtures. The selected aqueous solutions were then used in unsteady-state imbibition experiments conducted on miniature, water-wet Prairie Shell carbonate core samples. The experiments were performed utilizing a high-pressure, high-temperature two-phase core-flooding apparatus integrated with a high-resolution X-ray imaging system to acquire pore-scale fluid occupancy maps during the displacements. The results indicate that the injection of the selected CSN and CTN solutions into the carbonate samples under capillary-dominated flow regimes boosts the oil recovery by 12 and 2%, respectively, compared to those of the base waterflood. The VES solutions lowered the oil-water interfacial tension and exerted significant shear forces at the entrance of pores. The shear forces could exceed the threshold surface free energy required to deform oil globules, and consequently, large oil clusters were fragmented into smaller blobs and eventually produced from the pore space. The higher oil recovery by CSN flooding was attributed to its stronger viscoelastic properties. The VES injection under the viscous-dominated flow regime intensified the frequency of oil globule fragmentation. As a result, residual oil saturation values were sharply reduced in the rock samples from 44 to 55% during the capillary-dominated flows to approximately 8%. The above-mentioned observations were also verified using morphological analysis of residual oil clusters. The impacts of VES flooding on the pore-scale oil configuration and the fragmentation of large oil clusters were particularly evident at higher VES flow rates.

Pore-Scale Study of Wettability Alteration and Fluid Flow in Propped Fractures of Ultra-Tight Carbonates.

The in situ change in oil flow behavior inside propped fractures due to wettability alteration of proppant grains and fracture surfaces was thoroughly investigated for the first time in this study. A series of microscale flow experiments were performed in mixed-wet fractured and propped miniature ultra-tight carbonate cores where the effect of wettability on oil bridging and fracture oil layer integrity was probed during oil production. During the initial production, proppant wettability changed toward an intermediate-wet state (contact angle (CA) = 96°) while that of fracture surfaces became strongly oil-wet (CA = 139°). Consequently, the fracture oil layer grew in size on both fracture surfaces and imbibed into the proppant pack through piston-like displacement and pore body filling until oil bridges were formed during oil injection. However, subsequent waterflooding induced thinning and rupturing of those bridges due to the accompanying reduction in the threshold capillary pressure of the proppant at higher aging times. The in situ chemical treatment of the proppant by a cationic surfactant (dodecyl tri-methyl ammonium bromide) could reverse its wettability toward weakly water-wet state (CA = 78°) after oil solubilization from the sand grains followed by substitutive surfactant adsorption. Surfactant injection also impacted the wettability of the fracture surface due to oil solubilization, reducing its mean contact angle down to an intermediate range (CA = 99°). As a result, the following oil production cycle yielded a smaller fracture oil layer. The surfactant effect on proppant wettability lasted for 2 weeks while its effect on fracture wettability lasted for more than 6 weeks. Similar flow cycles were performed with an anionic nanoparticle (graphene quantum dot) with hydrogen bonding ability. The nanoparticle solution yielded a quick reduction of the proppant and fracture surface contact angles to nearly 77° and 115°, respectively. Proppant wettability alteration occurred because the nanoparticles self-assembled at the three-point contact region between adsorbed oil and quartz surfaces, leading to oil solubilization in intermediate-wet regions while oil-wet regions remained unchanged. Therefore, re-introducing oil into the fracture instantaneously re-instated the initial wettability state of proppant grains (CA = 88°), deeming the nanoparticle solution ineffective. This study revealed that oil production through hydraulic fractures can be enhanced by monitoring the wettability of the proppant pack. If the production has a high water cut, it is beneficial to use chemical agents that reduce the proppant contact angles to a weakly water-wet state in order to preserve the hydraulic conductivity of the oil layer.

Quantitative Predictions and Experimental Validation of Liquid-Vapor Interfacial Tension in Binary and Ternary Mixtures of Alkanes Using Molecular Dynamics Simulations.

Liquid-vapor interfacial properties of alkane mixtures present a challenge for experimental determination, especially under conditions relevant to the energy industry processes. Molecular dynamics (MD) simulations can accurately predict interfacial tensions (IFTs) for complex alkane mixtures under virtually any conditions, thereby alleviating the need for difficult and costly experiments. MD simulations with the CHARMM force field and empirical corrections for the IFT and pressure were used to obtain the IFT for three binary mixtures of ethane (with n-pentane, n-hexane, and n-nonane) and a ternary system (ethane/n-butane/n-decane) under a variety of conditions. The results were thoroughly validated against experimental data from the literature, and new original IFT data were collected using the pendant drop method. The simulations are able to reproduce the experimental IFT to better than 0.5 mN/m or 5% on average and within 1 mN/m or 10% in the worst case. IFTs for the studied three binary and ternary alkane mixtures were predicted for wide ranges of conditions with no known experimental data. Finally, using the MD simulation data, the reliability of the widely used empirical parachor model for predicting IFT was reaffirmed, and the significance of the empirical parameters examined to establish an optimal balance between the accuracy and broad applicability of the model.

Wettability reversal on oil-wet calcite surfaces: Experimental and computational investigations of the effect of the hydrophobic chain length of cationic surfactants.

HYPOTHESIS: Oil recovery from carbonate reservoirs is often low, in a large part due to the oil-wet state of the constituent rocks. Cationic surfactants are among the most effective compounds capable of reversing the carbonate wettability to more water-wet, which significantly enhances oil recovery. Screening for the most effective cationic surfactants can be facilitated by studying the effects of specific molecular properties, such as the hydrophobic chain length, on the wettability reversal efficiency using molecular dynamics (MD) simulations. EXPERIMENTS AND SIMULATIONS: Wettability reversal by quaternary ammonium cationic surfactants with varying hydrophobic chain length was studied by the combination of MD simulation and experimental contact angle measurements on oil-wet calcite chips. Both experiments and simulations also featured model oils consisting of different size hydrocarbons in order to explore the potential size-specific interactions between the surfactants and oil molecules. FINDINGS: We found strong correlation between the wettability reversal and the surfactant length, with the longer surfactants universally rendering calcite surfaces more water-wet. By contrast, the wettability reversal is independent of the model oil used, implying that the effect is not due to specific hydrocarbon size. Instead, the superior wettability reversal performance of the more hydrophobic surfactants is due to their greater affinity to the oil/brine interfaces.

Liquid-Vapor Interfacial Tension in Alkane Mixtures: Improving Predictive Capabilities of Molecular Dynamics Simulations.

The liquid-vapor interfacial properties of hydrocarbons and their mixtures are important factors in a wide range of industrial processes and applications. Determining these properties experimentally, however, is not only practically demanding, but many important properties, such as phase densities and compositions are not directly experimentally accessible, thus requiring the development of theoretical models. Molecular dynamics (MD) simulations, by contrast, are relatively straightforward even for the most complex of mixtures and directly provide all of the microscopic quantities for the studied systems. We have previously applied MD simulations to study the liquid-vapor equilibria of mixtures of hydrocarbons and CO2 that are particularly relevant to hydrocarbon recovery from geologic formations. In this study, we explore in more detail the robustness of the simulation methods with respect to the choice of the model system parameters, investigate the accuracy of the simulations in determining the key quantities: system pressure and interfacial tension (IFT), and, finally, devise a simple correction for achieving a much closer agreement between the simulated and experimental quantities. We perform extensive MD simulations for three mixtures, propane/n-pentane, propane/n-hexane, and CO2/n-pentane, using model systems from 1000 up to 100 000 molecules, and different simulation box dimensions to test for the sensitivity to finite-size effects. The results show that changing the system size and box dimensions does not significantly impact the accuracy of the simulations. Subsequently, we examine the accuracy of the MD simulations in determining the pressure and IFT for two pure hydrocarbon systems, n-pentane and n-heptane. Finally, we propose a simple linear correction formula for the pressures and IFTs obtained from the MD simulations that closely reproduce the experimental values for single components and mixtures of hydrocarbons. Our results enable the MD simulations to provide more accurate and reliable predictions of the interfacial properties, thereby reducing the need for challenging laboratory experiments.

Surfactant-induced wettability reversal on oil-wet calcite surfaces: Experimentation and molecular dynamics simulations with scaled-charges.

HYPOTHESIS: Surfactant flooding is the leading approach for reversing the wettability of oil-wet carbonate reservoirs, which is critical for the recovery of the remaining oil. Combination of molecular dynamics (MD) simulations with experiments on simplified model systems can uncover the molecular mechanisms of wettability reversal and identify key molecular properties for systematic design of new, effective chemical formulations for the enhanced oil recovery. EXPERIMENTS/SIMULATIONS: Wettability reversal by a series of surfactant solutions was studied experimentally using contact angle measurements on aged calcite chips, and a novel MD simulation methodology with scaled-charges that provides superior description of the ionic interactions in aqueous solutions. FINDINGS: The MD simulation results were in excellent agreement with the experiments. Cationic surfactants were the most effective in reversing the calcite wettability, resulting in complete detachment of the oil from the surface. Some nonionic surfactants also altered the wettability, but to a lesser degree, while the amphoteric and anionic surfactants had no effect. From the tested cationic surfactants, the double-tailed one was the least effective, but the experiments were inconclusive due to its poor solubility. Contributions of specific interactions to the wettability reversal process and implications for the design and optimization of surfactants for the enhanced oil recovery are discussed.

In-situ capillary pressure and wettability in natural porous media: Multi-scale experimentation and automated characterization using X-ray images.

HYPOTHESIS: Geometrical analyses of pore-scale fluid-fluid-rock interfaces have recently been used for in-situ characterization of capillary pressure and wettability in natural porous media. Nevertheless, more robust techniques and multi-scale, well-characterized experimental data are needed to rigorously validate these techniques and enhance their efficacy when applied to saturated porous media. EXPERIMENTS AND IMAGE ANALYSIS: We present two new techniques for automated measurements of in-situ capillary pressure and contact angle, which offer several advancements over previous methodologies. These approaches are methodically validated using synthetic data and X-ray images of capillary rise experiments, and subsequently, applied on pore-scale fluid occupancy maps of a miniature Berea sandstone sample obtained during steady-state drainage and imbibition flow experiments. FINDINGS: The results show encouraging agreement between the image-based capillary pressure-saturation function and its macroscopic counterpart obtained from a porous membrane experiment. However, unlike the macroscopic behavior, the micro-scale measurements demonstrate a nonmonotonic increase with saturation due to the intermittency of the pore-scale displacement events controlling the overall flow behavior. This is further explained using the pertinent micro-scale mechanisms such as Haines jumps. The new methods also enable one to generate in-situ contact angle distributions and distinguish between the advancing and receding values while automatically excluding invalid measurements.

Molecular Dynamics Simulations of the Vapor-Liquid Equilibria in CO2/n-Pentane, Propane/n-Pentane, and Propane/n-Hexane Binary Mixtures.

Molecular dynamics (MD) simulations were used to study vapor-liquid equilibrium interfacial properties of n-alkane and n-alkane/CO2 mixtures over a wide range of pressure and temperature conditions. The simulation methodology, based on CHARMM molecular mechanics force field with long-range Lennard-Jones potentials, was first validated against experimental interfacial tension (IFT) data for two pure n-alkanes (n-pentane and n-heptane). Subsequently, liquid-vapor equilibria of CO2/n-pentane, propane/n-pentane, and propane/n-hexane mixtures were investigated at temperatures from 296 to 403 K and pressures from 0.2 to 6 MPa. The IFT, liquid and vapor phase densities, and molecular compositions of the liquid and vapor phases and of the interface were analyzed. The calculated mixture IFTs were in excellent agreement with experiments. Likewise, calculated phase densities closely matched values obtained from the equation of state (EOS) fitted to the experimental data. Examination of the density profiles, particularly in the liquid-vapor transition regions, provided a molecular-level rationalization for the observed trends in the IFT as a function of both molecular composition and temperature. Finally, two variants of the empirical parachor model commonly used for predicting the IFT, the Weinaug-Katz and Hugill-Van Welsenes equations, were tested for their accuracy in reproducing the MD simulation results. The IFT prediction accuracies of both equations were nearly identical, implying that the simpler Weinaug-Katz model is sufficient to describe the IFT of the studied systems.

Wettability Reversal on Dolomite Surfaces by Divalent Ions and Surfactants: An Experimental and Molecular Dynamics Simulation Study.

Due to the importance of the dolomite mineral in carbonate reservoirs, the wettability characteristics of dolomite surfaces were studied with both experiments and molecular dynamics simulations. Contact angle measurements confirm that the dolomite surface can be rendered oil-wet by carboxylates (acidic components of crude oil) and that the cationic surfactant can reverse the oil-wetness more effectively than the anionic surfactant used in this study. The oil-wetness of an aged dolomite chip was reduced when treated with MgSO4 solution at 80 °C, while CaCl2, MgCl2, and Na2SO4 solutions did not produce any significant wettability alteration. The effects of surfactants and divalent ions, Ca2+, Mg2+, and SO42- (also referred to as Smart Water ions), were simulated with two model dolomite surfaces containing point defects and step vacancies, respectively. The results indicate that the cationic surfactant can weaken the attraction between the oil phase and the carboxylates, while the anionic surfactant tends to maintain the oil-wetness of the dolomite surface by replacing the carboxylates through competitive adsorption. All Ca2+, Mg2+, and SO42- ions can act as potential determining ions, and the detachment of carboxylates is due to the repulsion from SO42- ions drawn close to the surface in the presence of adsorbed Mg2+.

Sub-nanometer scale investigation of in situ wettability using environmental transmission electron microscopy.

HYPOTHESIS: Contact angle measurements alongside Young's equation have been frequently used to quantitatively characterize the wettabilities of solid surfaces. In the literature, the Wenzel and Cassie-Baxter models have been proposed to account for surface roughness and chemical heterogeneity, while precursor film models have been developed to account for stress singularity. However, the majority of these models were derived based on theoretical analysis or indirect experimental measurements. We hypothesize that sub-nanometer-scale in situ investigations will elucidate additional complexities that impact wettability characterization. EXPERIMENTS: To develop further insights into in situ wettability, we provide the first direct experimental observation of fluid-solid occupancies at three-phase contacts at sub-nanometer resolution, using environmental transmission electron microscopy. FINDINGS: Considering the partially spreading phenomenon and capillarity, we provide an improved physics-based interpretation of measuring the sub-nanometer-scale contact angle at the inflection point of the fluid-fluid interface. The difference between this angle and the commonly-used apparent one measured at a lower resolution is also discussed. Furthermore, we provide direct experimental evidence for the density differences between the adsorbed wetting film and the bulk wetting phase. For the effect of surface roughness, the applicability of the Wenzel model is discussed based on the observed in situ solid-fluid occupancies.

Effect of Pore Size Distribution on Capillary Condensation in Nanoporous Media.

The occurrence of capillary condensation is often ignored in many naturally occurring nanoporous media, such as shale rock, simply because their isotherms do not adhere to the prescribed shapes presented in the literature. In particular, it is apparent from the literature that most shale isotherms do not display a clear capillary condensation step, which is commonly observed for much simpler adsorbents, such as MCM-41. We contend that the absence of this step from the isotherms for natural adsorbents is not due to the absence of nanoconfinement-induced phase behavior. Rather, it is due to the broad pore size distribution characteristic of such materials. By mechanically mixing different sizes of MCM-41 together and measuring isotherms for propane and n-butane in them at a variety of temperatures, we show that phase behavior in different pore sizes is additive and suppresses the commonly observed appearance of capillary condensation. By comparing the isotherms in the mixtures of MCM-41 to those measured in single pore sizes of MCM-41, we develop correlations, using the Lorentzian function, that make the determinations of porosity and fluid density from the mixture isotherms straightforward.

Effects of Surfactant Charge and Molecular Structure on Wettability Alteration of Calcite: Insights from Molecular Dynamics Simulations.

Wettability alteration of oil-wet calcite by surfactants was studied by means of molecular dynamics (MD) simulations. The simulations use the recently developed model for positively charged calcite surface, whose oil-wet state originates from binding of negatively charged carboxylate molecules contained in the oil, consistently with the bulk of the available experimental data. The ability to alter the surface wettability, which can be directly quantified by the release of the surface-bound carboxylates, is tested for nine different surfactants of all charge types-cationic, anionic, nonionic, and zwitterionic-and compared to that of brine. It was found that only the cationic surfactants are able to detach the organic carboxylates more efficiently than brine, while the neutral and anionic surfactants do not seem to have any measurable effect on the wettability. The outperformance of the cationic surfactants is generally consistent with the majority of previously published experimental observations. The data also point toward a consistently better performance of single-tailed cationic surfactants over the two-tailed structure. Molecular mechanism of the wettability alteration by different types of surfactants is discussed, along with the implications of the results for the design of new surfactant formulations for the enhanced oil recovery.

Pore-scale experimental investigation of oil recovery enhancement in oil-wet carbonates using carbonaceous nanofluids.

This study investigates the pore-scale displacement mechanisms of crude oil in aged carbonate rocks using novel engineered carbon nanosheets (E-CNS) derived from sub-bituminous coal. The nanosheets, synthesized by a simple top-down technique, were stable in brine without any additional chemicals. Owing to their amphiphilic nature and nano-size, they exhibited dual properties of surfactants and nanoparticles and reduced the oil/brine interfacial tension (IFT) from 14.6 to 5.5 mN/m. X-ray micro-computed tomography coupled with miniature core-flooding was used to evaluate their ability to enhance oil recovery. Pore-scale displacement mechanisms were investigated using in-situ contact angle measurements, oil ganglia distribution analysis, and three-dimensional visualization of fluid occupancy maps in pores of different sizes. Analysis of these maps at the end of various flooding stages revealed that the nanofluid invaded into medium and small pores that were inaccessible to base brine. IFT reduction was identified as the main displacement mechanism responsible for oil recovery during 1 to 8 pore volumes (PVs) of nanofluid injection. Subsequently, wettability alteration was the dominant mechanism during the injection of 8 and 32 PVs, decreasing the average contact angle from 134° (oil wet) to 85° (neutral wet). In-situ saturation data reveals that flooding with only 0.1 wt% of E-CNS in brine resulted in incremental oil production of 20%, highlighting the significant potential of this nanofluid as a recovery agent.

Quantitative analysis of phase topology evolution during three-phase displacements in porous media.

Multiphase flow in subsurface formations is the essence of aquifer remediation and petroleum recovery processes, where the phase mobilities are greatly influenced by phase topologies. Yet, flow models rarely utilize quantified phase topologies due to the limited availability of such data. Here, we conducted cutting-edge experiments using a micromodel together with a state-of-the-art automated imaging system to capture images with high temporal and areal resolution to characterize the phase topologies for three-phase displacements. The micromodel setup used in this study is a close replica of flow in natural rocks as the resulting three-phase saturation routes agrees well with results of rocks core floods. The injection sequence was repeated with different fluids to compare the effects of fluid properties on phase topologies. The resulting high fidelity images were used to calculate topological parameters such as Euler characteristic, the contact area between phases, flowing sub-phase, wetted rock surface area and saturations. We show that the trend of topological parameters helps to identify the dominant pore scale mechanisms. Furthermore, the developed workflow assists with verification of the microfluidic devices and mechanistic scaling of the microfluidic results to the desired condition.

Wettability of Calcite Surfaces: Impacts of Brine Ionic Composition and Oil Phase Polarity at Elevated Temperature and Pressure Conditions.

The interactions among the polar components of oil, aqueous phase ions, and carbonate minerals, as well as their subsequent effects on surface wettability, can significantly impact the fluid distribution and recovery in a hydrocarbon reservoir. In this study, we investigate the adsorption/desorption of molecules from oils with different levels of polarity on calcite surfaces during different displacement processes under elevated pressure and temperature conditions. We measured dynamic contact angles (CA) on untreated and aged calcite substrates using brines with different salinities and compositions and model oils, that is, mixtures of varying concentrations of stearic acid (SA) and n-decane. In particular, the impacts of the concentrations of Ca2+, SO42-, and OH- ions on the adsorption phenomena were explored. For the nonpolar oil, increasing brine salinity or removing Ca2+ ions from the aqueous phase impacted the potentials of oil-brine and brine-mineral interfaces and shifted the wettability of calcite surface toward more water-wet conditions. In the presence of polar oil, the adsorption of the polar components controls the surface wettability. Higher concentrations of Ca2+/SO42- could facilitate/obstruct the polar component adsorption and thus increase/decrease the dynamic oil-water CAs. It is also observed that the brine salinity does not impact the wettability if excess SA is added to the oil phase, that is, if the oil phase is strongly polar. Moreover, the adsorption of SA on the calcite surface under experimental conditions is found to be reversible during the displacement events. The surface energy calculation for the adsorption process indicates that the surface coverage of calcite by SA is more sensitive to the presence of Ca2+ in brine than the concentration of polar components in oil. We also conducted several experiments on calcite substrates aged with SA. The measurements demonstrate that the adsorbed SA molecules are detached when the aged mineral surface is exposed to a lower-salinity brine at high temperatures, and the SA molecules could be adsorbed back on the surface once the displacement is halted.

A positively charged calcite surface model for molecular dynamics studies of wettability alteration.

A new model for a positively charged calcite surface was developed to allow realistic molecular dynamics studies of wettability alteration on carbonate rocks. The surface charge was introduced in a manner consistent with the underlying calcite geochemistry and with the conclusions of recent quantum mechanical studies. The simulations using the new surface model demonstrate that the experimentally observed wettability behavior of calcite is represented correctly. In particular, the model surface became oil-wet due to the adsorption of the carboxylate species. Furthermore, the oil-wet conditions were reversed more effectively by a cationic surfactant than by an anionic one, in agreement with the majority of experimental observations. Finally, with simulated smart water, the well-documented wettability alteration abilities of Ca2+ and SO42- could be explained by the formation of ion-pairs and competitive adsorption onto the surface, respectively. The simulation results with the new surface model conceptually agree with the electric double layer expansion being the predominant mechanism for the low salinity effect in oil recovery enhancement. The proposed calcite surface model will benefit future simulation studies on the wettability characteristics of carbonate rocks, and facilitate the design and optimizations of chemical agents and formulations to enhance the oil recovery from carbonate reservoirs.