Oil recovery performances of surfactant solutions by capillary imbibition

Critical parameters playing a role in oil recovery by capillary imbibition of surfactant solutions were studied. Experiments conducted on sandstone and carbonate samples using different oil and surfactant types were evaluated for surfactant selection. In this evaluation interfacial tension (IFT), surfactant type, solubility characteristics of surfactants, rock type, initial water (pre-wet rock), and surfactant concentration were considered. In addition to these, a new technique was adopted to facilitate the surfactant screening process. This technique is based on assigning inorganic and organic property values and plotting organic conception diagrams (OCD) for surfactants. OCD defines the property of a compound in terms of physical chemistry in such a way that the property that depends much on the van der Waals force is called "organic" and the one that depends much on electric affinity is called "inorganic." Correlations between the capillary imbibition recovery performance and the properties of surfactant and oil (organic value (OV), inorganic value (IV), and IFT of surfactant solutions, oil viscosity, and surfactant type) were obtained. These correlations are expected to be useful in selecting the proper surfactant for improved oil recovery as well as identifying the effects of surfactant properties on the capillary imbibition performance.     

Mutual influence of cetyltrimethylammonium bromide and Triton X-100 on their adsorption at the water–air interface

On the basis of surface tension values of the aqueous solution of cetyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) mixtures measured at 293 K as a function of CTAB or TX-100 concentration at constant TX-100 or CTAB concentration, respectively, the real surface area occupied by these surfactants at the water–air interface was established which is inaccessible in the literature. It appeared that at the concentration of the CTAB and TX-100 mixture in the bulk phase corresponding to the unsaturated monolayer at the water air-interface this area is the same as in the monolayer formed by the single surfactant at the same concentration as in the mixture. In the saturated mixed monolayer at this interface the area occupied by both surfactants is lower than that in the single surfactant monolayer corresponding to the same concentration in the aqueous solution. However, the decrease of the CTAB adsorption is lower than that of TX-100 and the total area occupied by the mixture of surfactants is also lower than that of the single one. The area of particular surfactants in the mixed saturated monolayer changes as a function of TX-100 and CTAB mixture concentration and at the concentrations close to CMC or higher the area occupied by both surfactants is the same. The changes of the composition of the mixed surface monolayer are connected with the synergetic effect in the reduction of the water surface tension by the adsorption of CTAB and TX-100 at the water–air interface. This effect was confirmed by the values of the standard Gibbs free energy of adsorption of both individual surfactants and their mixtures with different compositions in the bulk phase determined by using the Langmuir equation if RT instead of nRT was applied in this equation.     

Influence of Nonionic Surfactant on Alkaline Hydrolysis of Methyl Violet Catalyzed by Cetyltrimethylammonium Bromide

The alkaline hydrolysis of methyl violet (MV) was studied by spectrophotometric method under pseudo-first-order conditions at 298 K. Cationic surfactant cetyltrimethylammonium bromide (CTAB) catalyzed the reaction. Addition of nonionic surfactant Triton X-100 (TX-100) exhibited significant influence on the CTAB catalyzed reaction by lowering the extent of catalysis. The kinetic data were analyzed by Piszkiewicz model of positive cooperativity. Linear Hill-type plots were generated with indices of cooperativity values greater than unity. The effect of counterions on the reaction rates was also studied in the presence of cationic surfactant (CTAB) and cationic–nonionic mixed surfactants (CTAB/TX-100).     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

UV-Visible Spectrometric Study and Micellar Enhanced Ultrafiltration of Alizarin Red S Dye

Ultraviolet spectrometric study of alizarin red S (ARS) showed the substantial change in dye spectra by cationic CTAB as compared to anionic SDS and nonionic TX-100 surfactant. High spectral change by CTAB confirms the anionic nature of ARS dye and thus ARS-CTAB complex formation takes place due to electrostatic force of attraction. A little spectral change by SDS is the result of similarly charged repulsive forces that overcome weak hydrophobic-hydrophobic interaction between dye and surfactant micelles. TX-100 exhibited moderate spectral effect responsive to weak hydrophobic-hydrophobic interaction alone. MEUF study of ARS dye justified the spectral changes and dye rejection percentage (R) decreases in the following order: cationic > nonionic > anionic surfactant. Permeate flux (J) slightly decreases in presence of CTAB and it remains virtually constant for both SDS and TX-100. Addition of copper salt (i.e., CuCl₂) in dye-CTAB complex solution, favors rejection (%) removing dye and copper simultaneously via micellar enhanced ultrafiltration.     

The Wettability Alteration and the Effect of Initial Rock Wettability on Oil Recovery in Surfactant-based Enhanced Oil Recovery Processes

Wettablity alteration of rock surface is an important mechanism for surfactant-based enhanced oil recovery (EOR) processes. Two salt and temperature-tolerant surfactant formulations were developed based on the conditions of high temperature (97–120°C) and high salinity (20 × 10⁴ mg/L) reservoirs where a surfactant-based EOR process is attempted. Both the two sufactant formulations can achieve ultralow interfacial tension level (≤10^?3 mN/m) with crude oil after aging for 125 days at reservoir conditions. Wettability alteration of core slices induced by the two surfactant formulations was evalutated by measuring contact angles. Core flooding experiments were carried out to study the influence of initial rock wettabilities on oil recovery in the crude oil/surfactant/formation water/rock system. The results indicated that the two formulations could turn oil-wet core slices into water-wet at 90–120°C and 20 × 10⁴ mg/L salinity, while the water-wet core slices retained their hydrophilic nature. The core flooding experiments showed that the water-wet cores could yield higher oil recovery compared with the oil-wet cores in water flooding, surfactant, and subsequent water flooding process. The two surfactant formulations could successfully yield additional oil recovery in both oil-wet and water-wet cores.     

Role of surfactants in clouding phenomenon of imipramine hydrochloride

The clouding behavior of tricyclic antidepressant drug imipramine hydrochloride (IMP) in aqueous solution has been studied in presence of surfactants. A pH increase in the presence as well as in the absence of surfactants decreased the CP. Drug molecules become neutral at high pH and therefore head–head repulsion decreases which lead to CP decrease. Addition of non-ionic and cationic surfactants increased the CP whereas anionic surfactants showed a peaked profile. Effect of CTAB/TX-100 at different fixed drug concentrations showed that at all surfactant concentrations the CP value was higher for higher drug concentrations. However, variation of pH produced opposite effect: CP at all CTAB/TX-100 concentrations decreased with increasing pH. All results are interpreted in terms of increase in hydrophobicity or hydrophilicity of micelles on addition of surfactants.     

Experimental investigation on spontaneous counter‐current imbibition in water‐wet natural reservoir sandstone core using MRI

Counter‐current imbibition is a process whereby a wetting phase spontaneously imbibes into a porous media, displacing the non‐wetting phase. This process is considered an important oil recovery mechanism during water flooding in fractured oil reservoirs. In this study, the dynamic process of counter‐current imbibition for a natural reservoir sandstone core with an all‐face‐open boundary condition was monitored using magnetic resonance imaging (MRI). A series of images and relaxation time T₁ spectra were acquired. The movement of water spontaneously entering the core sample while oil escapes, the spatial distribution of oil and water, and the in situ saturation change of oil and water in porous media can be accurately detected using MRI. MRI assists the direct evaluation of the basic mechanisms of imbibitions. Experimental results suggest the remaining oil was trapped in some large pores because of the capillary pressure, and the oil recovery in some large‐pore regions is lower than that in some small‐pore regions at the end of imbibition. Experimental findings show a close agreement between conventional material balance and oil recovery determined from MRI. The in situ oil recovery data agree well with the empirical models. The observations from MRI images could provide test cases to enable the development of mathematical models and to facilitate the evaluation of the proposed imbibition mechanisms. Copyright © 2016 John Wiley & Sons, Ltd.     

Interaction of poly(vinylpyrrolidone) with cationic and nonionic surfactants in aqueous solution studied by <Superscript>1</Superscript>H NMR

Aqueous solutions of surfactant at various concentrations with 0.2% poly(vinylpyrrolidone) (PVP) were studied by ¹H NMR methods, including relaxation time and self-diffusion coefficient measurements and two-dimensional nuclear Overhauser enhancement spectroscopy. Two surfactants were concerned: cationic cetyltrimethylammonium bromide (CTAB) and nonionic Triton X-100 (TX-100). In the presence of 0.2% PVP, the variation of the T ₂ values of CTAB protons is similar to that in the absence of PVP. Relaxation times of PVP protons are not significantly affected by the increasing concentration of CTAB. This indicates that no interaction between PVP and CTAB could be detected. However, in the presence of 0.2% PVP, TX-100 micelles are formed at a concentration lower than its normal critical micellization concentration. According to the results of relaxation time measurement of water protons, the presence of 0.2% PVP also induces the contraction of the hydrophilic layer of the TX-100 micelle. This indicates some interaction between PVP and TX-100, but the mechanism of this interaction needs further investigation.     

Studies in the phase behavior of the microemulsions formed by mixed cationic and nonionic surfactants

The middle-phase behavior for the systems of cetyltrimethylammonium bromide (CTAB)/poly-ethyleneglycol-9-monododecyl ether (AEO₉)/alcohol/oil/brine and CTAB/octylphenolpolyoxyethylene-10-ether (Triton X-100)/alcohol/oil/brine have been studied with ɛ-β fishlike phase diagram method. The interfacial layer composition was determined, and some significant physicochemical parameters are derived from the hydrophilic-lipophilic balance plane equation. The effects of different alcohols, oils, temperature and inorganic salt (NaCl) on the middle-phase behavior of microemulsion formed by composite CTAB/AEO₉ systems were also investigated systematically. The effects of different factors on the phase behavior of microemulsions formed by CTAB/AEO₉ and CTAB/TX-100 systems were compared. The results suggest that the solubilization of CTAB/AEO₉ microemulsion is higher than that of CTAB/TX-100 system under the same conditions.     

Synergistic effect of mixed anionic and cationic surfactant systems on the interfacial tension of crude oil-water and enhanced oil recovery

Surfactant based enhanced oil recovery (EOR) is an interesting area of research for several petroleum researchers. In the present work, individual and mixed systems of anionic and cationic surfactants consisting of sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB) in different molar ratios were tested for their synergistic effect on the crude oil-water interfacial tension (IFT) and enhanced oil recovery performance. The combination of these two surfactant systems showed a higher surface activity as compared to individual surfactants. The effect of mixed surfactant systems on the IFT and critical micellar concentration (CMC) is strongly depends on molar ratios of the two surfactant. Much lower CMC values were observed in case of mixed surfactant systems prepared at different molar ratios as compared to individual surfactant systems. The lowest CMC value was found when the molar concentration of SDS was higher than the CTAB. When the individual and mixed surfacant systems were tested for EOR performance through flooding experiments, higher ultimate oil recovery was obtained from mixed surfactant flooding compared to individual surfactants. Combination of SDS and CTAB or probably other anionic-cationic surfactants show synergism with substantial ability to reduce crude oil water IFT and can be a promising EOR method.     

Influence of the interfacial adsorptions on the imbibition of aqueous solutions of low concentration of the non-ionic surfactant Triton X-100 into calcium fluoride porous medium

The imbibition of aqueous solution of Triton X-100 in porous columns of calcium fluoride has been carried out in order to investigate the surfactant influence on the capillary rise. Experiments have consisted of the measurement of the increase in the weight of the porous columns caused by the imbibition of the solutions. From their analysis, it has been found that the capillary rise velocity does not depend on the surfactant concentration, and that imbibition of these solutions behaves as in the case of water. This unexpected finding can not be attributed to depletion of the surfactant molecules from the advancing meniscus, since this effect can not be caused by the adsorption at the solid. This lack of surfactant adsorption on the solid is precisely the reason that justifies the observed behaviour. So, it has been proved that the driving force for the capillary rise movement will remain unaltered despite the surfactant addition whenever the free energies of the solid interfaces are not modified by the adsorption on the solid. Therefore, it is concluded from this study that only if adsorption on the solid happened, the imbibition could be influenced by the surfactant concentration.     

Influence of surfactants on the adsorption and elektrokinetic properties of the system: guar gum/manganese dioxide

The adsorption of non-ionic polysaccharide—guar gum (GG) in the presence or absence of the surfactants: anionic SDS, cationic CTAB, nonionic TX-100 and their equimolar mixtures SDS/TX-100, CTAB/TX-100 from the electrolyte solutions (NaCl, CaCl₂) on the manganese dioxide surface (MnO₂) was studied. The increase of GG adsorption amount in the presence of surfactants was observed in every measured system. This increase results from formation of complexes between the GG and the surfactant molecules. This observation was confirmed by the determination of the influence of GG on surfactants adsorption on the MnO₂ surface. The increase of GG adsorption on MnO₂ was the largest in the presence of the surfactant mixtures (CTAB/TX-100; SDS/TX-100) which is the evidence of the synergetic effect. The smallest amounts of adsorption were obtained in the presence of TX-100, which results from non-ionic character of this surface active agent. In the case of single surfactant solution CTAB has the best efficiency in increasing the amount of GG adsorption on MnO₂ which results from strong interactions with GG and also with the negatively charged surface of the adsorbent. In order to determine the electrokinetic properties of the system, the surface charge density of MnO₂ and the zeta potential measurements were performed in the presence of the GG macromolecules and the above mentioned surfactants and their mixtures. The obtained data showed that the adsorption of GG or GG/surfactants complexes on the manganese dioxide surface strongly influences the diffused part of the electrical double layer (EDL)—MnO₂/electrolyte solution, but has no influence on the compact part of the electric double layer. This is the evidence that the polymers chains are directly bonded with the surface of the solid and the surfactants molecules are present in the upper part of the EDL.     

Dynamics of capillary imbibition when surfactant, polymer, and hot water are used as aqueous phase for oil recovery

Capillary imbibition is an oil recovery mechanism in naturally fractured reservoirs if rock matrix is water wet and there is enough water in fractures in contact with matrix. It, however, may not yield an effective recovery under certain circumstances even if these conditions are maintained. Heavy matrix oil, high interfacial tension (IFT), oil-wet matrix sample, and limited contact area of matrix with water in fractures require additional effort to enhance the oil recovery by capillary imbibition. Chemicals and heat can be injected into naturally fractured reservoirs to improve the capillary imbibition recovery performance. With the involvement of low IFT fluid, heat, and polymer solution in the process, capillary imbibition dynamics may change and this entails an identification of the dynamics of the process through laboratory experiments before injection of these expensive fluids into oil reservoirs. In this study, the dynamics of capillary imbibition was studied experimentally. Static imbibition experiments were conducted on oil- and water-wet rock samples under different boundary conditions and saturated with different types of oil. The analyses were conducted using three indicators, namely the capillary imbibition rate, ultimate oil recovery, and shape of the recovery profile. Based on these indicators, the dynamics of capillary imbibition of different aqueous phases were evaluated for different oil types and matrix properties. The conditions that cause weak or strong capillary imbibition were identified.     

Formation and microstructure transition of F127/TX-100 complex

Formation and structure transition of the complex composed of triblock copolymer F127 and nonionic surfactant TX-100 have been investigated by 1H NMR spectroscopy, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Three TX-100 concentration regions are identified, within which TX-100/20 mg/mL F127 complex undergoes different temperature-induced structure transitions. In low concentration region (< 9.42 mM), F127 single molecular species (unimers) wrap around TX-100 micelles forming F127/TX-100 complex with TX-100 micelle as the skeleton at a lower temperature (5 degrees C), and the skeleton transfers to F127 micelle at higher temperature (40 degrees C); in intermediate TX-100 concentration region (9.42-94.85 mM), the skeleton of F127/TX-100 complex transfers from TX-100 micelle successively into F127 micelle and TX-100 micelle again upon heating. The interaction of F127 with TX-100 is saturated in high TX-100 concentration region (> 157.57 mM), and free TX-100 micelles coexist with larger clusters of F127/TX-100 complexes. In addition, TX-100-induced F127/TX-100 complex formation and structure transition are also investigated at constant temperatures. The results show that within 5-10 degrees C, F127 unimers mainly adsorb on the surface of TX-100 micelles just like normal water soluble polymers; in the temperature region of 15-25 degrees C, TX-100 micelles prompts F127 micelle formation. Within 30-40 degrees C, TX-100 inserts into F127 micelles leading to the breakdown of F127 aggregates at higher TX-100 concentrations, and the obtained unimers thread through TX-100 micelles forming complex with TX-100 micelle as skeleton.     

Polarographic behavior of nicotinamide in surfactant media and its determination in cetyltrimethylammonium bromide surfactant system

The behavior of nicotinamide has been studied by differential pulse polarography and cyclic voltammetry in the presence of certain ionic and nonionic surfactants, viz. cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and Triton X-100 (TX-100). The cathodic peak potential (E(p(c))) and peak current (I(p(c))) of nicotinamide were found to be remarkably dependent on the charge and concentration of the surfactant. The presence of SDS and that of TX-100 cause a shift in peak potential and a change in peak current of nicotinamide. In the presence of the cationic surfactant, CTAB, an enhancement in the sensitivity of nicotinamide was observed. A sharp peak with more than two-fold increase in current was used to determine the limit of detection and linear working range using the differential pulse polarographic technique. The present method was successfully used for the simultaneous determination of nicotinamide and pyridoxine hydrochloride, and for the determination of nicotinamide in multivitamin pharmaceutical preparations.     

Effect of Gas-Wetness of Cores on Imbibition

Gas-wetness of cores plays an important role on imbibition. Gas-wetness of cores, treated by various concentration fluorocarbon polymer Zonyl8740 (aq), was measured by the captive bubble. Subsequently, co-current and counter-current spontaneous imbibition were conducted on the various gas-wet cores both in air/wate and air/oil systems. Experimental results showed that, with the increase of concentration of Zonyl8740 solutions, gas-wetting ability against liquid on the cores gets stronger, gas recovery decreases, and the trapped gas saturation increases. Meanwhile, on the cores treated by the same concentration Zonyl8740 solution, air/water systems have a stronger gas-wettability than that of air/oil systems.      

Molecular behavior and synergistic effects between sodium dodecylbenzene sulfonate and Triton X-100 at oil/water interface

Significant synergistic effects between sodium dodecylbenzene sulfonate (SDBS) and nonionic nonylphenol polyethylene oxyether, Triton X-100 (TX-100), at the oil/water interface have been investigated by experimental methods and computer simulation. The influences of surfactant concentration, salinity, and the ratio of the two surfactants on the interfacial tension were investigated by conventional interfacial tension methods. A dissipative particle dynamics (DPD) method was used to simulate the adsorption properties of SDBS and TX-100 at the oil/water interface. The experiment and simulation results indicate that ultralow (lower than 10(-3) mN m(-1)) interfacial tension can be obtained at high salinity and very low surfactant concentration. Different distributions of surfactants in the interface and the bulk solution corresponding to the change of salinity have been demonstrated by simulation. Also by computer simulation, we have observed that either SDBS or TX-100 is not distributed uniformly over the interface. Rather, the interfacial layer contains large cavities between SDBS clusters filled with TX-100 clusters. This inhomogeneous distribution helps to enhancing our understanding of the synergistic interaction of the different surfactants. The simulation conclusions are consistent with the experimental results.     

The interplay of hydrophobic and electrostatic effects in the surfactant-induced aggregation/deaggregation of chlorin p6

The aggregation/deaggregation of chlorin p6 with the surfactants CTAB, SDS, and TX 100 have been studied by using absorption, fluorescence, and light scattering techniques. The ionic surfactants are found to cause aggregation of fluorophore at submicellar concentrations. The aggregates dissolve at higher surfactant concentrations to yield micellized monomers. This is rationalized by the interplay of electrostatic and hydrophobic effects. A prominent pH effect is observed in the ionic surfactant induced aggregation process as the charge on the fluorophore is controlled by the pH of the medium. Interestingly, the neutral TX-100 also induces aggregation of chlorin p6 at low concentrations, indicating that hydrophobic effects by themselves can cause aggregation unless there is a hindrance by repulsive electrostatic effects.     

Spectral studies of N-nonyl acridine orange in anionic, cationic and neutral surfactants

The spectroscopic and photophysical properties of N-nonyl acridine orange - a metachromatic dye useful as a mitochondrial probe in living cells - are reported in water and microheterogeneous media: anionic sodium dodecylsulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and neutral octylophenylpolyoxyethylene ether (TX-100). The spectral changes of N-nonyl acridine orange were observed in the presence of varying amount of SDS, CTAB and TX-100 and indicated formation of a dye-surfactant complex. The spectral changes were also regarded to be caused by the incorporation of dye molecules to micelles. It was proved by calculated values K(b) and f in the following order: K(bTX-100)>K(bCTAB)>K(bSDS) and f(TX-100)>f(CTAB)>f(SDS). NAO binds to the micelle regardless the micellar charge. There are two types of interactions between NAO and micelles: hydrophobic and electrostatic. The hydrophobic interactions play a dominant role in binding of the dye to neutral TX-100. The unexpected fact of the binding NAO to cationic CTAB can be explained by a dominant role of hydrophobic interactions over electrostatic repulsion. Therefore, the affinity of NAO to CTAB is smaller than TX-100. Electrostatic interactions play an important role in binding of NAO to anionic micelles SDS. We observed a prolonged fluorescence lifetime after formation of the dye-surfactant complex tau(SDS)>tau(TX-100)>tau(CTAB)>tau(water), the dye being protected against water in this environment. TX-100 is found to stabilize the excited state of NAO which is more polar than the ground state. Spectroscopic and photophysical properties of NAO will be helpful for a better understanding of the nature of binding and distribution inside mammalian cells.