Study of the effect of acidic species on wettability alteration of calcite surfaces by measuring partitioning coefficients, IFT and contact angles

SPE Journal ◽  
2019 ◽  
Vol 24 (03) ◽  
pp. 1092-1107 ◽  
Author(s):  
M.. Tagavifar ◽  
M.. Balhoff ◽  
K.. Mohanty ◽  
G. A. Pope

Summary Surfactants induce spontaneous imbibition of water into oil-wet porous media by wettability alteration and interfacial-tension (IFT) reduction. Although the dependence of imbibition on wettability alteration is well-understood, the role of IFT is not as clear. This is partly because, at low IFT values, most water/oil/amphiphile(s) mixtures form emulsions and/or microemulsions, suggesting that the imbibition is accompanied by a phase change, which has been neglected or incorrectly accounted for in previous studies. In this paper, spontaneous displacement of oil from oil-wet porous media by microemulsion-forming surfactants is investigated through simulations and the results are compared with existing experimental data for low-permeability cores with different aspect ratios and permeabilities. Microemulsion viscosity and oil contact angles, with and without surfactant, were measured to better initialize and constrain the simulation model. Results show that with such processes, the imbibition rate and the oil recovery scale differently with core dimensions. Specifically, the rate of imbibition is faster in cores with larger diameter and height, but the recovery factor is smaller when the core aspect ratio deviates considerably from unity. With regard to the mechanism of water uptake, our results suggest, for the first time, that (i) microemulsion formation (i.e., fluid/fluid interface phenomenon) is fast and favored over the wettability alteration (i.e., rock-surface phenomenon) in short times; (ii) a complete wettability transition from an oil-wet to a mixed microemulsion-wet and surfactant-wet state always occurs at ultralow IFT; (iii) wettability alteration causes a more uniform imbibition profile along the core but creates a more diffused imbibition front; and (iv) total emulsification is a strong assumption and fails to describe the dynamics and the scaling of imbibition. Wettability alteration affects the imbibition dynamics locally by changing the composition path, and at a distance by changing the flow behavior. Simulations predict that even though water is not initially present, it forms inside the core. The implications of these results for optimizing the design of low-IFT imbibition are discussed.


SPE Journal ◽  
2015 ◽  
Vol 20 (04) ◽  
pp. 767-783 ◽  
Author(s):  
C.. Qiao ◽  
L.. Li ◽  
R.T.. T. Johns ◽  
J.. Xu

Summary Injection of chemically tuned brines into carbonate reservoirs has been reported to enhance oil recovery by 5–30% original oil in place (OOIP) in coreflooding experiments and field tests. One proposed mechanism for this improved oil recovery (IOR) is wettability alteration of rock from oil-wet or mixed-wet to more-water-wet conditions. Modeling of wettability-alteration experiments, however, is challenging because of the complex interactions among ions in the brine and crude oil on the solid surface. In this research, we developed a multiphase and multicomponent reactive transport model that explicitly takes into account wettability alteration from these geochemical interactions in carbonate reservoirs. Published experimental data suggest that desorption of acidic-oil components from rock surfaces make carbonate rocks more water-wet. One widely accepted mechanism is that sulfate (SO42−) replaces the adsorbed carboxylic group from the rock surface, whereas cations (Ca2+, Mg2+) decrease the oil-surface potential. In the proposed mechanistic model, we used a reaction network that captures the competitive surface reactions among carboxylic groups, cations, and sulfate. These reactions control the wetting fractions and contact angles, which subsequently determine the capillary pressure, relative permeabilities, and residual oil saturations. The developed model was first tuned with experimental data from the Stevns Klint chalk and then used to predict oil recovery for additional untuned experiments under a variety of conditions where IOR increased by as much as 30% OOIP, depending on salinity and oil acidity. The numerical results showed that an increase in sulfate concentration can lead to an IOR of more than 40% OOIP, whereas cations such as Ca2+ have a relatively minor effect on recovery (approximately 5% OOIP). Physical parameters, including the total surface area of the rock and the diffusion coefficients, control the rate of recovery, but not the final oil recovery. The simulation results further demonstrate that the optimum brine formulations for chalk are those with relatively abundant SO42− (0.096 mol/kg water), moderate concentrations of cations, and low salinity (total ionic strength of less than 0.2 mol/kg water). These findings are consistent with the experimental data reported in the literature. The new model provides a powerful tool to predict the IOR potential of chemically tuned waterflooding in carbonate reservoirs under different scenarios. To the best of our knowledge, this is the first model that explicitly and mechanistically couples multiphase flow and multicomponent surface complexation with wettability alteration and oil recovery for carbonate rocks specifically.


Energies ◽  
2020 ◽  
Vol 13 (21) ◽  
pp. 5594
Author(s):  
Nilesh Kumar Jha ◽  
Maxim Lebedev ◽  
Stefan Iglauer ◽  
Jitendra S. Sangwai ◽  
Mohammad Sarmadivaleh

Wettability of surfaces remains of paramount importance for understanding various natural and artificial colloidal and interfacial phenomena at various length and time scales. One of the problems discussed in this work is the wettability alteration of a three-phase system comprising high salinity brine as the aqueous phase, Doddington sandstone as porous rock, and decane as the nonaqueous phase liquid. The study utilizes the technique of in situ contact angle measurements of the several 2D projections of the identified 3D oil phase droplets from the 3D images of the saturated sandstone miniature core plugs obtained by X-ray microcomputed tomography (micro-CT). Earlier works that utilize in situ contact angles measurements were carried out for a single plane. The saturated rock samples were scanned at initial saturation conditions and after aging for 21 days. This study at ambient conditions reveals that it is possible to change the initially intermediate water-wet conditions of the sandstone rock surface to a weakly water wetting state on aging by alkanes using induced polarization at the interface. The study adds to the understanding of initial wettability conditions as well as the oil migration process of the paraffinic oil-bearing sandstone reservoirs. Further, it complements the knowledge of the wettability alteration of the rock surface due to chemisorption, usually done by nonrepresentative technique of silanization of rock surface in experimental investigations.


2014 ◽  
Vol 962-965 ◽  
pp. 539-543
Author(s):  
Zi Yuan Qi ◽  
Ye Fei Wang ◽  
Hai Yang Yu ◽  
Xiao Li Xu

In order to study the effect of surfactants on wettability of quartz surface, the dynamic contact angles of different surfactants on water-wet and oil-wet quartz surfaces were measured. The experimental results showed that the advancing contact angles of cationic surfactants, anionic surfactants and nonionic surfactants on oil-wet quartz surfaces decrease with the increase of surfactant concentrations; the wettability of water-wet quartz plates remains water-wet after treated by all three kinds of surfactants. Surfactants can reverse the wettability from oil-wet to water-wet at low concentrations; The electrostatic force, hydrophobic force and the attraction between surfactant and polar components of crude oil are the key interactions in the wettability alteration process.


1973 ◽  
Vol 13 (04) ◽  
pp. 221-232 ◽  
Author(s):  
N.R. Morrow ◽  
P.J. Cram ◽  
F.G. McCaffery

Abstract Various nitrogen-, oxygen- and sulfur-containing compounds native to crude oils were screened for their effect on wettability as measured by contact angle. Solid substrates of quartz, calcite, and dolomite crystals were used to represent reservoir rock surfaces. With water and decane as liquids, contact angles were measured after a given polar compound was added to the oil phase. Contact angles measured at the two types of carbonate surfaces were generally similar. None of the nitrogen or sulfur compounds studied gave contact angles greater than 66 degrees on either quartz or carbonates. Of the oxygen-containing compounds, octanoic acid gave the widest range of contact angle - 0 degrees to 145 degrees on dolomite - over a molar concentration range up to 0.1. Capillary - pressure and relative-permeability curves were obtained for water and solutions of octanoic acid in oil, using packings of powdered dolomite as the porous medium. Because of a slow reaction between dolomite and octanoic acid, which was not revealed by standard contact angle studies, special precautions were needed to ensure satisfactory wettability control during displacement tests. Capillary-pressure drainage curves were measured at six contact angles, ranging from 0 degrees to 140 degrees. Drainage-imbibition cycles for three packings of distinctly different particle size were measured at contact angles of 0 degrees and 49 degrees. The effect of contact angle on imbibition capillary pressures was close to that found previously for porous polytetra-fluoroethylene, whereas there was comparatively polytetra-fluoroethylene, whereas there was comparatively less effect on drainage behavior-steady-state relative permeability curves exhibited distinct differences for contact angles of 15 degrees, 100 degrees and 155 degrees. Introduction Waterflooding is the most successful and widely applied improved recovery technique. Its application in Alberta has, on the average, more than doubled the recovery obtained by primary depletion. However, even after waterflooding, it is estimated that two-thirds of the discovered oil remains unrecovered. Interfacial forces acting during waterflooding lead to the entrapment of large quantities of residual oil in the swept zones. Considerable attention has been paid to recovering this oil through new recovery methods in which the interface is eliminated as in miscible processes, or the interfacial tension is drastically lowered, as in surfactant floods. Such processes involve a high initial cost for an injected solvent or surfactant bank. Recently released information on a variety of such improved recovery techniques has not been altogether encouraging with regard to developing economical processes. A distinct alternative to eliminating the interface is to understand it and learn how it can be manipulated to give increased waterflood recoveries. A prospect for improved recovery at interfacial tensions of the order normally encountered in reservoirs lies in a favorable adjustment of wettability by incorporating small amounts of low-cost additives in the floodwater. A first step in developing the technology of improved recovery by wettability alteration is to determine the effect of wettability alteration on displacement in systems of uniform wettability. It has been shown that, even in the "near miscible" surfactant processes, wettability can still have a significant influence on the extent to which interfacial tension must be lowered in order to mobilize residual oil. At the time when waterflooding first found widespread use, wettability was recognized as a variable that might well have a significant influence on recovery performance. Reservoir wettability and the role of wettability in displacement has been the subject of some 50 or so publications. Even so, many aspects of wettability are not well understood and there is no general agreement on a satisfactory method of characterizing it. Opinions as to the optimum wettability condition for recovery cover the spectrum from strongly water-wet through weakly water-wet or intermediately wet to strongly oil-wet. It has recently been suggested that a mixed wettability condition can give high ultimate recoveries. SPEJ P. 221


SPE Journal ◽  
2020 ◽  
Vol 25 (05) ◽  
pp. 2615-2631 ◽  
Author(s):  
Mehdi Mohammadi ◽  
Siavash Riahi

Summary Waterflooding is known as an affordable method to enhance oil recovery after primary depletion. However, the chemical incompatibility between injected water and the water in the reservoir may cause the formation of mineral scales. The most effective method for managing such a problem is to use a variety of scale inhibitors (SIs) along with a waterflooding plan. It is necessary to perform a comprehensive study on the incompatibility scaling issue for the candidate-brine/SI formulations, and also their effect on the reservoir-rock/fluid characteristics. In this study, both in the absence and presence of polymeric, phosphonate, and polyphosphonate SIs, the scaling tendency (ST) of different brines is evaluated through experimental and simulation works. Drop-shape analysis (DSA), environmental-scanning-electronic-microscopy (ESEM) observation, energy-dispersive X-ray (EDX) analysis, and microemulsion phase behavior are also used to study the effect of different brine/SI formulations on the rock/fluid and fluid/fluid interactions, through wettability and interfacial-tension (IFT) evaluation. In summary, sulfate (SO42−) was identified as the most problematic ion in the formulation of injected water that causes the formation of solid scales upon mixing with the cation-rich formation water (FW). In the case of SIs, solid precipitation was shifted toward a lower value, with more pronounced effects at higher SI concentrations. At different ionic compositions, the inhibition efficiency (IE%) of all SIs ranged from 16 to 50% at [SI]  = 20 ppm and 38 to 81% at [SI] = 50 ppm. In general, phosphonates worked better (i.e., higher IE value) than polymeric SI. Measuring contact angles along with ESEM/EDX data also illustrated the positive effect of SIs on the wettability alteration of the aged carbonate substrates. In the absence of SIs, the contact angles for different brines were in the range of 70° ≤ θ ≤ 104°, whereas these values fell between 35 and 80° for systems containing 50 ppm of SI. In addition, phase-behavior study and IFT measurement illustrated a salinity-dependence effect of SIs on the interfacial behavior of the oil/water system.


Resources ◽  
2018 ◽  
Vol 7 (4) ◽  
pp. 75
Author(s):  
Sina Rezaei Gomari ◽  
Kamal Elyasi Gomari ◽  
Meez Islam ◽  
David Hughes

Tertiary recovery is directly dependent on the alteration in wettability and interfacial tension (IFT), hence releasing the trapped oil from rock pore spaces. Bio-surfactant water flooding to mobilise residual oil in reservoirs is a new and developing prospect that can be used more often in future due to its environmentally friendly nature and economic advantages. In this work, the impact of rhamnolipids as water soluble bio-surfactant solutions on the interfacial activities of saline water and the wettability of carbonate rock are studied at elevated temperature. The effectiveness of the bio-surfactant as a rock wettability modifier is analysed in the presence of different salinities, in particular SO42− ions. The reason for the focus on SO42− is its high affinity towards calcite surfaces, and hence its ability to intervene strongly on bio-surfactant performance. To achieve the objectives of this study, the oil-wet calcite samples at elevated temperature were put through a washing process that included bio-surfactant solutions in seawater at various concentrations of sodium sulphate ions, where the measurement of the contact angles of each sample after treatment and the IFT between the oil model and the washing solutions were taken. The obtained results illustrated that bio-surfactants (rhamnolipids) with incremental concentrations of SO42− ions in sea water (up to three times higher than the original ion concentration) can lower the IFT, and assessed changing the rocks towards greater water-wettability. This study reveals that the alteration of SO42− ions had a greater impact on the wettability alteration, whereas rhamnolipids were better at reducing the IFT between the oil phase and the aqueous phase. This study also looked at temperatures of 50 °C and 70 °C, which demonstrated undesired influences on the wettability and IFT. Bio-surfactants at high temperature showed less interfacial activity, thus indicating that rhamnolipids are not active at high temperatures, while the addition of SO42− shows a continuous decrease in the contact angle and IFT measurements at high temperature.


2015 ◽  
Vol 1120-1121 ◽  
pp. 369-377 ◽  
Author(s):  
Jia Feng Jin ◽  
Yan Ling Wang ◽  
Fei Liu

Wettability is one of most important characteristics for governing the flow and distribution of reservoir fluids in the porous media,the wetting and spreading behavior of liquids on the solid surfaces changes if the wettability of solid surface is altered. Recent studies show the spreading behavior of liquids on solid surface can be significantly improved after nanofluid treatment. In order to investigate the influence of wettability alternation on enhancing oil recovery after nanofluid treatment,flushing oil experiment and contact angle measurement were conducted in the laboratory. The first experiment involved flushing crude oil with the nanofluid and conventional surfactants, respectively. In the second case, the contact angles of oil phase in nanofluid (conventional surfactant solutions)-crude oil-slide systems were measured after treating 36 hours. The results indicated that nanofluid can produce a better flushing efficiency compared with that of conventional surfactant, and the contact angles of oil phase increased from 33° to 118° after nanofluid treatment in nanofluid/crude-oil/slide system. The mechanism of enhanced oil recovery of nanofluid is mainly wettability alternation.


2018 ◽  
Vol 115 (36) ◽  
pp. 8901-8906 ◽  
Author(s):  
Ahmed AlRatrout ◽  
Martin J. Blunt ◽  
Branko Bijeljic

A quantitative in situ characterization of the impact of surface roughness on wettability in porous media is currently lacking. We use reservoir condition micrometer-resolution X-ray tomography combined with automated methods for the measurement of contact angle, interfacial curvature, and surface roughness to examine fluid/fluid and fluid/solid interfaces inside a porous material. We study oil and water in the pore space of limestone from a giant producing oilfield, acquiring millions of measurements of curvature and contact angle on three millimeter-sized samples. We identify a distinct wetting state with a broad distribution of contact angle at the submillimeter scale with a mix of water-wet and water-repellent regions. Importantly, this state allows both fluid phases to flow simultaneously over a wide range of saturation. We establish that, in media that are largely water wet, the interfacial curvature does not depend on solid surface roughness, quantified as the local deviation from a plane. However, where there has been a significant wettability alteration, rougher surfaces are associated with lower contact angles and higher interfacial curvature. The variation of both contact angle and interfacial curvature increases with the local degree of roughness. We hypothesize that this mixed wettability may also be seen in biological systems to facilitate the simultaneous flow of water and gases; furthermore, wettability-altering agents could be used in both geological systems and material science to design a mixed-wetting state with optimal process performance.


SPE Journal ◽  
2020 ◽  
Vol 25 (04) ◽  
pp. 1884-1894
Author(s):  
Zuoli Li ◽  
Subhash Ayirala ◽  
Rubia Mariath ◽  
Abdulkareem AlSofi ◽  
Zhenghe Xu ◽  
...  

Summary Polymer enhances the volumetric sweep efficiency through the increased viscosity of injection water and subsequently results in enhanced oil recovery. Most of the reported experimental studies focused on only evaluating polymer viscosifying characteristics and their associated significance for achieving adequate mobility control in porous media. The microscale effects of polymer on wettability alteration in carbonates are rarely studied. In this experimental investigation, the wettability of carbonates in the presence of polymer was measured using contact angle tests. In addition, the adhesion force between carbonate and crude oil droplets in polymer solutions was determined using a custom-designed integrated thin-film drainage apparatus equipped with a bimorph sensor. The liberation kinetics of crude oil from carbonate surfaces were also measured by an optical microscope-based liberation cell to understand the wettability alteration effects on oil recovery. All the experiments, except the adhesion force, which was measured at room temperature due to the restriction of bimorph sensor, were conducted at both ambient and elevated temperatures (70°C) using a sulfonated polyacrylamide polymer (SPAM) (at 500 and 700 ppm) in high-salinity injection water. Deionized (DI) water was used as a baseline to provide a representative comparison with the high-salinity brine. The contact angles of crude oil droplets on a carbonate surface were highest in DI water and decreased in brine. The addition of polymer decreased the contact angle further, with higher concentrations of polymer resulting in a lower contact angle. The adhesion force between crude oil and carbonate showed good agreement with contact angle data, and the oil adhesion was smallest on the carbonate surface in the presence of polymer. The crude oil liberation from the carbonate surface by flooding with brine and polymer was found to be more efficient at elevated temperature than at ambient temperature, consistent with lower contact angles measured in these aqueous solutions at high temperature. The equilibrium oil liberation degree with polymer solutions increased by more than two times when the temperature was increased from 23 to 70°C. The higher liberation degree obtained with polymer solutions also correlated well with the lowest adhesion force measured between crude oil and carbonate in the presence of polymer. These consistent results obtained from different experimental techniques indicated that the oil recovery improvements observed with polymer in dynamic liberation tests are not only related to the increase in water viscosity but are also due to favorable changes in wettability as inferred from both contact angle and adhesion force measurements. This experimental study, for the first time, characterized the microscale effects of polymer on wettability alteration and crude oil liberation in carbonates. The favorable effect of polymer on wettability alteration in carbonates revealed from this study has not been reported in the literature, and it can become a novel addition to the existing knowledge.


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