Phase Behavior Studies of Two Model Surfactant Systems

1982 ◽  
Vol 22 (01) ◽  
pp. 53-60 ◽  
Author(s):  
William J. Benton ◽  
Natoli John ◽  
Syed Qutubuddin ◽  
Surajit Mukherjee ◽  
Clarence M. Miller
Keyword(s):  
Aqueous Solutions ◽  
Phase Boundary ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Develop Model ◽  
Middle Phase ◽  
Lower Phase ◽  
Interfacial Tensions ◽  
Petroleum Sulfonate ◽  
Surfactant Systems

William J. Benton, Carnegie-Mellon U. John Natoli, Carnegie-Mellon U. Qutubuddin, Syed SPE, Carnegie-Mellon U. Mukherjee, Surajit, Carnegie-Mellon U. Miller, Clarence M., SPE, Carnegie-Mellon U. Fort Jr., Tomlinson, Carnegie-Mellon U. Abstract Phase behavior studies were carried out for two systems containing pure surfactants but exhibiting behavior similar to that of commercial petroleum sulfonates. One system contained the isomerically pure surfactant sodium-8-phenyl-n-hexadecyl-n-sulfonate (Texas 1). The other contained sodium dodecyl sulfate (SDS). Additional components used in both systems were various pure short-chain alcohols, NaCl brine and n-decane. Aqueous solutions containing surfactant, cosurfactant, and NaCl were studied over a wide range of compositions with polarizing and modulation contrast microscopy, as well as the polarized light screening technique. Viscosity measurements were conducted on selected scans of the Texas 1 system. Maxima and minima of the scans were correlated with textural changes observed with microscopy. The aqueous solutions were contacted with equal volumes of n-decane, and phase behavior and interfacial tensions were determined. The middle microemulsion phase was found to be oil continuous close to the upper phase boundary and water continuous close to the lower phase boundary. Both the Texas 1 and SDS systems showed similar behavior in that the middle microemulsion phase was observed over the entire range of surfactant concentrations studied. Introduction Surfactant systems usually consisting of petroleum sulfonate, an alcohol, salt, and water have been used for enhanced oil recovery. Various parameters important to oil recovery by surfactant flooding, such as interfacial tension and viscosity, are related strongly to the phase behavior of the microemulsion systems. The relationship of ultralow interfacial tensions to phase separation has been treated in our laboratory. The recovery of petroleum from laboratory cores and field tests appears to be related directly to phase behavior. It is important to understand phase behavior to identify the mechanisms involved and improve the efficiency of the oil-recovery process. The physicochemical aspects of the phase behavior of microemulsion systems containing commercial petroleum sulfonates as surfactants have been well documented by Healy and Reed and others. However, the systems studied were not pure, and the commercial surfactants sometimes contained as much as 40% inactive ingredients. There is a need to develop model microemulsion systems using pure components. Such systems would provide an experimental platform for verifying or interpreting the implications of any model for the phase behavior of multicomponent microemulsion systems and also allow the behavior of commercial systems to be predicted and understood. The objective of our work has been to fulfill these needs. Microemulsions have been classified as lower phase (l), upper phase (u), or middle phase (m) in equilibrium with excess oil, excess brine, or both excess oil and brine, respectively. Transitions among these phases have been studied as functions of salinity, alcohol concentration, temperature, etc. The middle-phase microemulsion is particularly significant because microemulsion/excess brine and microemulsion/excess oil tensions can be ultra low simultaneously. The concept of an optimal parameter as proposed originally by Reed and Healy when equal amounts of oil and brine are solubilized in the middle phase has been followed in this paper. We have shown earlier that the structure of petroleum sulfonate solutions exhibits a general pattern of variation with salinity. SPEJ P. 53^

Phase Boundaries of Microemulsion Systems as a Way of Characterizing Hydrocarbon Mixtures

1981 ◽  
Vol 21 (06) ◽  
pp. 763-770 ◽  
Author(s):  
Kishor D. Shah ◽  
Don W. Green ◽  
Michael J. Michnick ◽  
G. Paul Willhite ◽  
Ronald E. Terry
Keyword(s):  
Crude Oil ◽  
Phase Boundary ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Single Phase ◽  
Carbon Number ◽  
Phase Boundaries ◽  
Titration Method ◽  
Lower Phase ◽  
Surfactant System

Abstract Phase behavior of microemulsions composed of TRS 10-80, brine (10.6 mg/g NaCl), isopropyl alcohol, and mixtures of pure hydrocarbons was studied to determine the location of phase boundaries of the single-phase microemulsion region. Studies were conducted on pseudoternary phase diagrams where the pseudocomponents were isopropanol, brine, and a constant ratio of surfactant to hydrocarbon (S/H). Phase boundaries were determined be the titration method developed by Bowcott and Schulman, which was extended to systems of interest for oil recovery by Dominguez et al.The titration method involves the addition of brine to a single-phase microemulsion until phase separation occurs. Then the system is titrated to transparency by addition of isopropanol. Dominguez et al. demonstrated the applicability of the titration method for systems containing pure alkanes. They found upper and lower phase boundaries (high and low alcohol concentrations) for the microemulsion regions on S/H pseudoternary diagrams that were represented by linear relationships between the volume of alcohol and the volume of brine required to attain a single-phase microemulsion. This region, termed Region 4, bounded by linear phase boundaries, extends over a wide range of brine concentrations including regions of interest to enhanced oil-recovery processes. The research reported in this paper extends the work of Dominguez et al. to mixtures of pure hydrocarbons. The locations of the lower phase boundaries for Region 4 were determined for four types of mixtures prepared with pure hydrocarbons ranging from C6 to C18.In all phase behavior experiments, the lower phase boundary of Region 4 was a straight line when volume of alcohol was plotted against volume of brine. Furthermore, the slope of this phase boundary was found to be a linear function of alkane carbon number (ACN) for pure hydrocarbons and equivalent alkane carbon number (EACN) for mixtures of pure hydrocarbons.The correlation of a property of the phase diagram (the slope of the lower phase boundary) with EACN suggests a new approach to characterization of hydrocarbon/surfactant systems. In our experience, the EACN determined from phase behavior studies is more reproducible than the EACN determined from methods involving measurements of interfacial tensions. This method has potential for characterization of surfactant/hydrocarbon systems for complex mixtures of hydrocarbons, including crude oils. Introduction The design of a surfactant system for an enhanced oil-recovery application typically requires much effort, expense, and time. The surfactant system, usually consisting of a petroleum sulfonate and an alcohol dissolved in a brine solution, must be tailormade for a given crude oil/reservoir brine system where it will be applied. The process in finding the optimal system involves varying the components in the surfactant system in compatibility tests, phase behavior studies, physical property measurements, and displacement tests in both Berea and actual reservoir rock.One of the most important considerations in this screening procedure is matching the sulfonate to the crude oil of interest. This can be difficult since both the sulfonate and the crude oil are complex mixtures of pure components. It would be advantageous if each could be characterized by some physical property. SPEJ P. 763^

Importance of lignosulfonates in petroleum recovery operations

1981 ◽  
Vol 59 (13) ◽  
pp. 1938-1943 ◽  
Author(s):  
Graham Neale ◽  
Vladimir Hornof ◽  
Christopher Chiwetelu
Keyword(s):  
Crude Oil ◽  
Oil Recovery ◽  
Phase Behaviour ◽  
Oil Fields ◽  
Potential Importance ◽  
Mixed Surfactant ◽  
Interfacial Tensions ◽  
Mixed Surfactant Systems ◽  
Petroleum Sulfonate ◽  
Surfactant Systems

This paper reviews the potential importance of aqueous lignosulfonate solutions in the recovery of petroleum from existing partially depleted oil fields. The surfactant qualities of lignosulfonates are described and their ability to interact synergistically with petroleum sulfonate surfactants (which are currently popular in the industry) to produce ultra-low interfacial tensions with crude oil is discussed. The phase behaviour characteristics and oil recovery efficacies of these mixed surfactant systems are also examined.

Optimum Formulation of Surfactant/Water/Oil Systems for Minimum Interfacial Tension or Phase Behavior

1979 ◽  
Vol 19 (02) ◽  
pp. 107-115 ◽  
Author(s):  
J.L. Salager ◽  
J.C. Morgan ◽  
R.S. Schechter ◽  
W.H. Wade ◽  
E. Vasquez
Keyword(s):  
Molecular Weight ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Middle Phase ◽  
Interfacial Tensions ◽  
Three Phase ◽  
Optimum Formulation ◽  
The Subject ◽  
Tension State ◽  
Low Tension

Abstract A screening test used to help select surfactant systems potentially effective for oil recovery is to identify those formulations that yield middle-phase microemulsions when mixed with sufficient quantities of oil and brine. A correlation is presented to link these variables regarding their presented to link these variables regarding their contributions to middle-phase formation: structure of the sulfonated surfactant, alkane carbon number (ACN), and alcohol type and concentration. WOR and temperature effects are introduced as correction terms added to the empirical correlation.Sets of variables that give middle-phase microemulsions are shown as identical to those defining the low tension state without observable middle phases. This generally occurs for low surfactant phases. This generally occurs for low surfactant concentrations. Introduction Healy and Reed and Healy et al. have shown that the phase behavior of surfactant/brine/oil systems is a key factor in interpreting the performance of oil recovery by microemulsion performance of oil recovery by microemulsion processes. By systematically varying salinity, processes. By systematically varying salinity, they found low interfacial tensions and high solubilization of both oil and water in the microemulsion phase to occur in or near the salinity ranges giving phase to occur in or near the salinity ranges giving three phases. Since both low interfacial tensions and a high degree of solubilization are considered desirable for oil recovery, the conditions for three-phase formation assume added importance. Similar conclusions have been reported in other recent papers.Several investigators have considered the effect of different variables on the range of salinities for which three phases form. This optimum salinity (a more precise definition is given in a subsequent section) has been found to decrease with increasing surfactant molecular weight, and to increase with increasing chain length of the alcohol cosurfactant. Studies on the effect of alcohols by Jones and Dreher and Salter provided results similar to those reported by Hsieh and Shah.The interfacial tension at surfactant concentrations low enough so that a discernible third phase does not form has been the subject of considerable phase does not form has been the subject of considerable investigation regarding surfactant molecular weight and structure, oil ACN, salinity and surfactant concentration, and alcohol addition. A recent paper was a first attempt to tie together the low paper was a first attempt to tie together the low tension state observed at low surfactant concentrations and the three-phase region observed at higher surfactant concentrations. All indications point to an inextricable intertwining of phase point to an inextricable intertwining of phase behavior, surfactant partitioning, solubilization, and low tensions. This paper corroborates the equivalence of three-phase behavior and minimum tension as criteria for optimum formulation and presents a correlation that quantifies the trends presents a correlation that quantifies the trends observed previously. EXPERIMENTAL Aqueous phases containing surfactant, electrolyte (NaCl), and alcohol were contacted with an oil phase by shaking and allowed to stand until phase phase by shaking and allowed to stand until phase volumes became time independent for 2 days. All concentrations are expressed in grams of chemical per cubic centimeter of aqueous phase (g/cm3) per cubic centimeter of aqueous phase (g/cm3) before contacting with the hydrocarbon phase. Unless otherwise noted, the oil phase represents 20% of the initial total volume. All measurements, unless otherwise noted, were conducted at room temperature (25 plus or minus 1 degrees C). SPEJ p. 107

Criteria for Structuring Surfactants To Maximize Solubilization of Oil and Water: Part 1-Commercial Nonionics

1982 ◽  
Vol 22 (05) ◽  
pp. 743-749 ◽  
Author(s):  
Alain Graciaa ◽  
Lester N. Fortney ◽  
Robert S. Schechter ◽  
William H. Wade ◽  
Seang Yiv
Keyword(s):  
Phase Behavior ◽  
Oil Recovery ◽  
Nonionic Surfactants ◽  
Phase Region ◽  
Microemulsion System ◽  
Middle Phase ◽  
Optimal Salinity ◽  
Surfactant System ◽  
Hydrophilic Lipophilic Balance ◽  
Surfactant Systems

Abstract The phase behavior of nonionic surfactants having the same hydrophilic/lipophilic balance (HLB) but differing molecular weights has been studied. It is shown that the optimal alkane carbon number (ACN) depends on the HLB, but that increasing the hydrophobe molecular weight narrows the middle phase region, increases the solubilization parameter, and decreases the interfacial tension (IFT). We found that the width of the three-phase region is in simple inverse proportion to the solubilization parameter at optimal salinity and that the multiple of IFT times the square of the solubilization is a constant. We also found it possible to synthesize nonionics that rival anionics in the properties mentioned above. Introduction There is increasing evidence that the phase behavior of surfactant/oil/brine systems and the efficiency of oil recovery with micellar solutions are connected intimately. For instance, laboratory core floods have shown that surfactant systems exhibit maximum oil recovery at the optimal salinity. The concept of optimal salinity, introduced by Healy and Reed, is especially useful because it pen-nits screening of surfactant systems by relatively simple experiments requiring the observation of the number and the types of phases that coexist at equilibrium when surfactant/oil/brine mixtures are blended. Optimal salinity, defined as that middle-phase microemulsion system containing equal volumes of oil and water, is not difficult to determine, and, thus, conditions for the most efficient surfactant system can be established. It is now well known that many different surfactant systems have the same optimal salinity. Further, it generally has been assumed, but not definitely established by laboratory experiments that the preferred surfactant system, selected from a group of systems having the same optimal salinity, will be that which solubilizes the largest volume of oil and brine per unit mass of surfactant. We do not necessarily subscribe to this simple view. since there are many factors other than solubilization (such as surfactatant retention) that may influence oil recovery efficiency however, all other factors being equal, it is reasonable to attempt to maximize solubilization, especially because it has been found synonymous with minimal IFT's-an equally important factor governing effectiveness of oil recovery. This paper seeks to identify some surfactant structural features that will lead to increased solubilization and decreased IFT. We have addressed this important question in past publications but have met with only limited success. The difficulty has been that changing the surfactant structure dictates that a second corresponding change be made so that the resulting system would remain optimal. For instance, one can increase the length of the hydrocarbon tail of the surfactant molecule and at the same time compensate for this change either by decreasing the amount of hydrophobic alcohol added to the system or by decreasing the salinity of the system. The results obtained in this manner have remained difficult to interpret because all changes can and most often do alter the solubilization of oil and water in the middle-phase microemulsion. Therefore, it was not possible to separate that pan of the resulting solubilization change caused strictly by the modification of the surfactant structure. In the study discussed here, we made compensating changes in the surfactant structure, keeping all other variables fixed. For nonionic surfactants, compensating changes can be made in several ways. SPEJ P. 743^

Investigation of Three-Phase Regions Formed by Petroleum Sulfonate Systems

1981 ◽  
Vol 21 (05) ◽  
pp. 581-592 ◽  
Author(s):  
Creed E. Blevins ◽  
G. Paul Willhite ◽  
Michael J. Michnick
Keyword(s):  
Interfacial Tension ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Phase Region ◽  
Phase Boundaries ◽  
Middle Phase ◽  
Optimal Salinity ◽  
Petroleum Sulfonate ◽  
Recovery Processes ◽  
Three Phase

Abstract The three-phase region of the Witco TRS 10-80 sulfonate/nonane/isopropanol (IPA)/2.7% brine system was investigated in detail. A method is described to locate phase boundaries on pseudoternary diagrams, which are slices of the tetrahedron used to display phase boundaries of the four-component system.The three-phase region is wedge-like in shape extending from near the hydrocarbon apex to a point near 20% alcohol on the brine/alcohol edge of the tetrahedron. It was found to be triangular in cross section on pseudoternary diagrams of constant brine content, with its base toward the nonane/brine/IPA face. The apex of the three-phase region is a curved line where the M, H + M, and M + W regions meet. On this line, the microemulsion (M*) is saturated with hydrocarbon, brine, and alcohol for a particular sulfonate content. A H + M region exists above the three-phase region, and an M + W region exists below it.Relationships were found between the alcohol concentration of the middle phase and the sulfonate/alcohol and sulfonate/hydrocarbon ratios in the middle phase. These correlations define the curve that represents the locus of saturated microemulsions in the quaternary phase diagram. Alcohol contents of excess oil and brine phases also were correlated with alcohol in the middle phase.Pseudoternary diagrams for sulfonates are presented to provide insight into the evolution of the three-phase region with salinity. Surfactants include Mahogany AA, Phillips 51918, Suntech V, and Stepan Petrostep(TM) 500. Differences between phase diagrams follow trends inferred from comparisons of equivalent weights, mono-/disulfonate content, optimal salinity, and EPACNUS values. Introduction The displacement of oil from a porous rock by microemulsions is a complex process. As the microemulsion flows through the rock, it mixes with and/or solubilizes oil and water. The composition of the microemulsion is altered by adsorption of sulfonate, leading to expulsion of water and/or oil. Multiphase regions are encountered where phases may flow at different velocities depending on the fluid/rock interactions. Knowledge of phase behavior of microemulsion systems is required to understand the displacement mechanisms, to model process performance, and to select suitable compositions for injection.Microemulsions used in oil recovery processes consist of five components: oil, water, salt, surfactant (usually a petroleum sulfonate and a cosurfactant (usually an alcohol). Brine frequently is considered to be a pseudocomponent. When this assumption is valid, a microemulsion may be studied as a four-component system.Windsor developed a qualitative explanation and classification scheme for microemulsion phase behavior. Healy and Reed showed that Windsor's concepts were applicable to microemulsions used in oil recovery processes. Healy et al. introduced the concept of optimal salinity to define a particular characteristic of surfactant system. The optimal salinity for phase behavior was defined as the salinity where the middle phase of a three-phase system has equal solubility of oil and brine. They also found that optimal salinity determined in this manner was close to the salinity where the interfacial tension between the upper and middle phases was equal to the interfacial tension between the middle and lower phases.Salager et al. developed a correlation of optimal salinity data for a particular surfactant. SPEJ P. 581^

Interfacial Tension and Phase Behavior of Surfactant Systems

1978 ◽  
Vol 18 (04) ◽  
pp. 242-252 ◽  
Author(s):  
W.H. Wade ◽  
James C. Morgan ◽  
R.S. Schechter ◽  
J.K. Jacobson ◽  
J.L. Salager
Keyword(s):  
Molecular Weight ◽  
Interfacial Tension ◽  
Crude Oil ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Surfactant Concentration ◽  
Low Molecular Weight ◽  
Middle Phase ◽  
Surfactant Systems ◽  
Low Tension

Abstract The conditions necessary for optimum low tension and phase behavior at high surfactant concentrations are compared with those required at low surfactant concentrations, where solubilization effects are not usually visible. Major differences in tension behavior between the high and low concentration systems may be observed when the surfactant used contains a broad spectrum of molecular species, or if a higher molecular weight alcohol is present, but not otherwise in the systems studied. We compared the effects of a number of aliphatic alcohols on tension with phase behavior. An explanation of these results, and also of other observed parameter dependences, is proposed in terms of changes in surfactant chemical potential. Surfactant partitioning data is presented that supports this concept. Introduction Taber and Melrose and Brandner established that tertiary oil recovery by an immiscible flooding process should be possible at low capillary process should be possible at low capillary numbers. In practice, the required capillary number, which is a measure of the ratio of viscous to capillary forces governing displacement of trapped oil, may be achieved by lowering the oil/water interfacial tension to about 10(-3) dyne/cm, or less. Subsequent research has identified a number of surfactants that give tensions of this order with crude oils and hydrocarbon equivalents. Interfacial tension studies tended to fall into two groups. Work at low surfactant concentrations, typically 0.7 to 2 g/L, has established that a crude oil may be assigned an equivalent alkane carbon number. Using pure alkanes instead of crude oil has helped the study of system parameters affecting low tension behavior. Important parameters examined include surfactant molecular structure, and electrolyte concentration, surfactant concentration, surfactant molecular weight, and temperature. At higher surfactant concentrations, interfacial tension has been linked to the phase behavior of equilibrated systems. When an aqueous phase containing surfactant (typically 30 g/L), electrolyte, and low molecular weight alcohol is equilibrated with a hydrocarbon, the surfactant may partition largely into the oil phase, into the aqueous phase, or it may be included in a third (middle) phase containing both water and hydrocarbon. Low interfacial tensions occur when the solubilization of the surfactant-free phase (or phases) into the surfactant-containing phase is maximized. Maximum solubilization and minimum tensions have been shown to be associated with the formation of a middle phase. Both the high and low surfactant concentration studies have practical importance because even though a chemical flood starts at high concentration, degradation of the injected surfactant slug will move the system toward lower concentrations. This study investigates the relationship between tension minima found with low concentration systems, and low tensions found with equivalent systems at higher surfactants concentrations, particularly those in which third-phase formation occurs. Many of the systems studied here contain a low molecular weight alcohol, as do most surfactant systems described in the literature or proposed for actual oil recovery. Alcohol originally was added to surfactant systems to help surfactant solubility, but can affect tensions obtained with alkanes, and with refined oil. Few systematic studies of the influence of alcohol on tension behavior exist. Puerto and Gale noted that increasing the alcohol Puerto and Gale noted that increasing the alcohol molecular weight decreases the optimum salinity for maximum solubilization and lowest tensions. The same conclusions were reached by Hsieh and Shah, who also noted that branched alcohols had higher optimum salinities than straight-chain alcohols of the same molecular weight. Jones and Dreher reported equivalent solubilization results with various straight- and branched-chain alcohols. In this study, we fix the salinity of each system and instead vary the molecule; weight of the hydrocarbon phase. SPEJ P. 242

Effects of Hardness and Cosurfactant on Phase Behavior of Alcohol-Free Alkyl Propoxylated Sulfate Systems

SPE Journal ◽  
2015 ◽  
Vol 20 (05) ◽  
pp. 1145-1153 ◽  
Author(s):  
Maura C. Puerto ◽  
George J. Hirasaki ◽  
Clarence A. Miller ◽  
Carmen Reznik ◽  
Sheila Dubey ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Crude Oil ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Equilibrium Phase ◽  
Optimal Conditions ◽  
Lower Phase ◽  
Blend Ratio ◽  
Internal Olefin ◽  
Internal Olefin Sulfonate

Summary The effect of hardness was investigated on equilibrium phase behavior in the absence of alcohol for blends of three alcohol propoxy sulfates (APSs) with an internal olefin sulfonate (IOS) with a C15–18 chain length. Hard brines investigated were synthetic seawater (SW), 2*SW, and 3*SW, the last two with double and triple the total ionic content of SW with all ions present in the same relative proportions as in SW, respectively. Optimal blends of the APS/IOS systems formed microemulsions with n-octane that had high solubilization suitable for enhanced oil recovery at both ≈25°C and 50°C. However, oil-free aqueous solutions of the optimal blends in 2*SW and 3*SW, as well as in 8 and 12% NaCl solutions with similar ionic strengths, exhibited cloudiness and/or precipitation and were unsuitable for injection. In SW at 25°C, the aqueous solution of the optimal blend of C16–17 7 propylene oxide sulfate, made from a branched alcohol, and IOS15–18, was clear and suitable for injection. A salinity map prepared for blends of these surfactants illustrates how such maps facilitate the selection of injection compositions in which injection and reservoir salinities differ. The same APS was blended with other APSs and alcohol ethoxy sulfates (AESs) in SW at ≈25°C, yielding microemulsions with high n-octane solubilization and clear aqueous solutions at optimal conditions. Three APS/AES blends were found to form suitable microemulsions in SW with a crude oil at its reservoir temperature near 50°C. Optimal conditions were nearly the same for hard brines and NaCl solutions with similar ionic strengths between SW and 3*SW. Although the aqueous solutions for the optimal blends with crude oil were slightly cloudy, small changes in blend ratio led to formation of lower phase microemulsions with clear aqueous solutions. When injection and reservoir brines differ, it may be preferable to inject at such slightly underoptimum conditions to avoid generating upper phase, Winsor II, conditions produced by inevitable mixing of injected and formation brines.

scholarly journals The Importance of Microemulsion for the Surfactant Injection Process in Enhanced Oil Recovery

2021 ◽  
Author(s):  
Rini Setiati ◽  
Muhammad Taufiq Fathaddin ◽  
Aqlyna Fatahanissa
Keyword(s):  
Interfacial Tension ◽  
Enhanced Oil Recovery ◽  
Oil Recovery ◽  
Recovery Process ◽  
Injection System ◽  
Type I ◽  
Middle Phase ◽  
Interface Tension ◽  
Lower Phase ◽  
Injection Process

Microemulsion is the main parameter that determines the performance of a surfactant injection system. According to Myers, there are four main mechanisms in the enhanced oil recovery (EOR) surfactant injection process, namely interface tension between oil and surfactant, emulsification, decreased interfacial tension and wettability. In the EOR process, the three-phase regions can be classified as type I, upper-phase emulsion, type II, lower-phase emulsion and type III, middle-phase microemulsion. In the middle-phase emulsion, some of the surfactant grains blend with part of the oil phase so that the interfacial tension in the area is reduced. The decrease in interface tension results in the oil being more mobile to produce. Thus, microemulsion is an important parameter in the enhanced oil recovery process.

Evaluation of the Interfacial Tension Between a Microemulsion and the Excess Dispersed Phase

1981 ◽  
Vol 21 (05) ◽  
pp. 593-602 ◽  
Author(s):  
E. Ruckenstein
Keyword(s):  
Interfacial Tension ◽  
Oil Recovery ◽  
Phase Inversion ◽  
The Other ◽  
Dispersed Phase ◽  
Middle Phase ◽  
Inversion Point ◽  
Interfacial Tensions ◽  
Dispersed Medium ◽  
Oil Water

Abstract From a consideration of the thermodynamic stability of microemulsions, one can establish a relation between the interfacial tension y at the surface of the globules and the derivative, with respect to their radius re, of the entropy of dispersion of the globules in the continuous medium. Expressions for the entropy of dispersion are used to show that gamma is approximately proportional to kT/r2e, where k is Boltzmann's constant and T is the absolute temperature. Since the environment of the interface between the microemulsion and the excess dispersed medium is expected to be similar to that at the surface of the globules, these expressions are used to evaluate the interfacial tension between microemulsion and excess dispersed medium. Values between 10 and 10 dyne/cm that decrease with increasing radii are obtained, in agreement with the range found experimentally by various authors. The origin of the very small interfacial tensions rests ultimately in the adsorption of surfactant and cosurfactant on the interface between phases. The effect on the interfacial tension of fluctuations from one type of microemulsion to the other, which may occur near the phase inversion point, is discussed. Introduction The system composed of oil, water, surfactant, cosurfactant, and salt exhibits interesting phase equilibria. For sufficiently large concentrations of surfactant, a single phase can be formed either as a microemulsion or as a liquid crystal. In contrast, at moderate surfactant concentrations, two or three phases can coexist. For moderate amounts of salt (NaCl), an oil phase is in equilibrium with a water-continuous microemulsion, whereas for high salinity, an oil-continuous microemulsion coexists with a water phase. At intermediate salinity, a middle phase (probably a microemulsion) composed of oil, water, surfactants, and salt forms between excess water and oil phases. Extremely low interfacial tensions are found between the different phases, with the lowest occurring in the three-phase region. These systems have attracted attention because of their possible application to tertiary oil recovery. It has been shown that the displacement of oil is most effective at very low interfacial tensions.Microemulsions have been investigated with various experimental techniques, such as low-angle X-ray diffraction, light scattering, ultracentrifugation, electron microscopy, and viscosity measurements. These have shown that the dispersed phase consists of spherical droplets almost uniform in size. While it is reasonable to assume that the microemulsions coexisting with excess oil or water contain spherical globules of the dispersed medium, the structure of the middle-phase microemulsion is more complex. Experimental evidence obtained by means of ultracentrifugation indicates, however, that at the lower end of salinity the middle phase contains globules of oil in water, while at the higher end the middle phase is oil continuous. A phase inversion must occur, at an intermediate salinity, from a water-continuous to an oil-continuous microemulsion. The free energies of the two kinds of microemulsions are equal at the inversion point. Since their free energy of formation from the individual components is very small, small fluctuations, either of thermal origin or due to external perturbations, may produce changes from one type to the other in the vicinity of the inversion point. As a consequence, near this point, it is possible that the middle phase is composed of a constantly changing mosaic of regions of both kinds of microemulsions. SPEJ P. 593^

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