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^

Phase Behavior and Properties of a Petroleum Sulfonate Blend

1981 ◽  
Vol 21 (05) ◽  
pp. 573-580 ◽  
Author(s):  
J.H. Bae ◽  
C.B. Petrick
Keyword(s):  
Interfacial Tension ◽  
Crude Oil ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Surfactant Solution ◽  
Phase Region ◽  
Salinity Range ◽  
Equal Weight ◽  
Optimal Salinity ◽  
Petroleum Sulfonate

Abstract A sulfonate system composed of Stepan Petrostep TM 465, Petrostep 420, and 1-pentanol was investigated. The system was found to give ultralow interfacial tension against crude oil in a reasonable range of salinity and sulfonate concentrations. It also was found that sulfonate partitioned predominantly into the microemulsion phase. However, a significant amount also partitioned into water and, at high salinity, into the oil phase. On the other hand, the oil-soluble 1-pentanol partitioned mostly into oil and microemulsion phases.The interfacial tension between excess oil and water phases was ultralow, in the range of 10-3 mN/m. The tensions were close to and paralleled those between the middle and water phases. The trend remained the same even when the alcohol content changed. This means that in the salinity range that produces a three-phase region, below the optimal salinity, the water phase effectively displaces both oil and middle phases, even though the oil may not be displaced effectively by the middle phase. The implication is that, from an interfacial tension point of view, the oil recovery would be more favorable in the salinity range below the optimal salinity with the mixed petroleum sulfonate system used here. This was confirmed by oil recovery tests in Berea cores. It also was concluded that the change in viscosity upon microemulsion formation might have a significant influence on the surfactant flood performance. Introduction During a surfactant flood, the injected slug of surfactant solution undergoes complex changes as it traverses the reservoir. The surfactant solution is diluted by mixing with reservoir oil and brine and by depletion of surfactant due to retention. Also, the reservoir salinity rarely is the same as that of the injected solution. Moreover, there is chromatographic separation of sulfonate and cosurfactant.When phase equilibrium between oil, brine, and injected surfactant is reached in the front portion of the slug, a microemulsion phase is formed. This phase behavior and its importance in oil recovery have been the subject of numerous papers in recent years. The microemulsion phase formed in the reservoir contacts fresh reservoir brine and oil and undergoes further changes. All these changes are accompanied by property changes of the phases that affect oil recovery.The objective of this paper is to investigate the properties of a blend of commercial petroleum sulfonates and its behavior in different environments. The phase volume behavior and changes in the properties of different phases and their effects on oil recovery were studied. This work was done as part of the design of a surfactant process for a field application. Therefore, a crude oil was used as the hydrocarbon phase. Experimental Procedures A blend of Petrostep 465 and 420 from Stepan Chemical Co. was used as the surfactant. An equal weight of each sulfonate on a 100% active basis was mixed. 1-pentanol from Union Carbide Corp. was used as a cosurfactant. Unless otherwise stated, a 50g/kg sulfonate concentration was used in the solution. We used symbols to denote the formulation. The first number in the symbol indicates the 1-pentanol concentration; the last number indicates the NaCl concentration. Thus, 15 P 10 means that the solution consists of 50 g/kg sulfonate, 15 g/kg 1-pentanol, and 10 g/kg NaCl. The sulfonate blend first was mixed with alcohol, and then the required amount of NaCl brine was added to make the solution. SPEJ P. 573^

Mixing Rules for Optimum Phase-Behavior Formulations of Surfactant/Oil/Water Systems

1979 ◽  
Vol 19 (05) ◽  
pp. 271-278 ◽  
Author(s):  
J.L. Salager ◽  
M. Bourrel ◽  
R.S. Schechter ◽  
W.H. Wade
Keyword(s):  
Phase Behavior ◽  
Oil Recovery ◽  
Practical Interest ◽  
Phase Region ◽  
Salinity Range ◽  
Mixing Rules ◽  
Recovery Efficiency ◽  
Middle Phase ◽  
Rich Phase ◽  
Three Phase

Abstract Many formulations used in surfactant flooding involve blends of surfactants designed to glue the best oil-recovery efficiency. Because oil-recovery efficiency usually is presumed to relate closely to surfactant/brine/oil phase behavior, it is of interest to understand the effect of mixing surfactants or of mixing oils on this phase behavior.We show that a correlation defining optimal behavior as a function of salinity, alcohol type and concentration, temperature, WOR (water/oil ratio), and oil type can be extended to mixtures of sulfonated surfactants and to those of sulfonates with sulfates and of sulfonates with alkanoates, provided the proper mixing rules are observed. provided the proper mixing rules are observed. The mixing rules apply to some mixtures of anionic and nonionic surfactants, but not to all. These mixtures exhibit some properties that may be of practical interest, such as increased salinity and practical interest, such as increased salinity and temperature tolerance. Introduction Recent studies have shown that formulation of the surfactant/brine/oil system is a key factor governing the performance of microemulsions designed to recover residual oil. These studies demonstrate that all optimal formulations exhibit characteristic properties that are remarkably similar. In general, properties that are remarkably similar. In general, the optimal microemulsion can solubilize large quantities of oil and connate water; in the presence of excess quantities of oil and water, a third surfactant-rich middle phase is formed. The interfacial tensions (IFT's) between the excess phases and the surfactant-rich phase are both low - about 10 dyne/cm (10 mN/m). Given an oil/brine system from a particular reservoir, one can achieve this formulation by varying the surfactant or the cosurfactant. Different oils, brines, or temperatures require formulations correspondingly altered to maintain optimal conditions. Previous studies have shown that the three-phase region exists over a range of values when one parameter, such as cosurfactant concentration, parameter, such as cosurfactant concentration, salinity, temperature, etc., is varied systematically (often called a scan). Thus, some ambiguity may exist with regard to the selection of those parameters representing the optimal formulation. Clearly, the optimum is that which recovers the most oil. However, tests are laborious, difficult to reproduce precisely, and sensitive to other factors, such as precisely, and sensitive to other factors, such as mobility, surfactant retention, wettability, etc. Therefore, it is desirable to impose an alternative definition that can be used for screening, though the final design still is dictated by core floods.Healy and Reeds have shown that the optimal formulation for oil recovery closely corresponds to that for which the IFT's between the excess oil and water phases and the surfactant-rich phase are equal. An almost equivalent criterion also was shown to be that point in the three-phase region for which the volume of oil solubilized into the middle phase equals the volume of brine. Furthermore, Salager et al. have used still another criterion that seems to be essentially equivalent to those used by Healy and Reed - an optimal salinity is defined as the midpoint of the salinity range for which the system exhibits three phases.These criteria are useful because they permit the screening of microemulsion systems using simple laboratory tests. SPEJ P. 271

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^

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

Solution Properties and Phase Behavior of Ammonium Hexylene Octyl Succinate in Water and Water-Oil System

1970 ◽  
Vol 3 (1) ◽  
Author(s):  
Md. Hamidul Kabir ◽  
Ravshan Makhkamov ◽  
Shaila Kabir
Keyword(s):  
Critical Micelle Concentration ◽  
Phase Behavior ◽  
Liquid Crystalline ◽  
Carbon Number ◽  
Phase Region ◽  
Solution Properties ◽  
Middle Phase ◽  
Two Phase ◽  
Lamellar Liquid Crystal ◽  
Drug Ingredient

The solution properties and phase behavior of ammonium hexylene octyl succinate (HOS) was investigated in water and water-oil system. The critical micelle concentration (CMC) of HOS is lower than that of anionic surfactants having same carbon number in the lipophilic part. The phase diagrams of a water/ HOS system and water/ HOS/ C10EO8/ dodecane system were also constructed. Above critical micelle concentration, the surfactant forms a normal micellar solution (Wm) at a low surfactant concentration whereas a lamellar liquid crystalline phase (La) dominates over a wide region through the formation of a two-phase region (La+W) in the binary system. The lamellar phase is arranged in the form of a biocompatible vesicle which is very significant for the drug delivery system. The surfactant tends to be hydrophilic when it is mixed with C10EO8 and a middle-phase microemulsion (D) is appeared in the water-surfactant-dodecane system where both the water and oil soluble drug ingredient can be incorporated in the form of a dispersion. Hence, mixing can tune the hydrophile-lipophile properties of the surfactant. Key words: Ammonium hexylene octyl succinate, mixed surfactant, lamellar liquid crystal, middle-phase microemulsion. Dhaka Univ. J. Pharm. Sci. Vol.3(1-2) 2004 The full text is of this article is available at the Dhaka Univ. J. Pharm. Sci. website

The Effect of Several Polymers on the Phase Behavior of Micellar Fluids

1982 ◽  
Vol 22 (06) ◽  
pp. 816-830 ◽  
Author(s):  
Gary A. Pope ◽  
Kerming Tsaur ◽  
Robert S. Schechter ◽  
Ben Wang
Keyword(s):  
Phase Behavior ◽  
Nonionic Surfactants ◽  
Polymer Concentration ◽  
Salinity Range ◽  
Lower Phase ◽  
Optimal Salinity ◽  
Rich Phase ◽  
Three Phase ◽  
Phase Systems ◽  
Increasing Temperature

Abstract We made static measurements of the phase volumes of mixtures of surfactant, polymer, alcohol, water, oil, sodium chloride, and in some cases polymer additives. We also made a limited number of viscosity, phase concentration, and interfacial tension (IFT) measurements. The purpose was to determine systematically the effect of various polymers on the phase behavior of various surfactant formulations. We made measurements with and without oil (n-octane and n-octane/benzene mixtures) across a range of salinity appropriate to the particular surfactant at temperatures between 24 and 75 degrees C. Introduction The oil-free (i.e., no added oil) solutions showed a characteristic phase separation into an aqueous surfactant-rich phase and an aqueous polymer-rich phase at some sufficiently high salinity (NaCl concentration), which we call the critical electrolyte concentration (CEC). The CEC was found to be a characteristic of a given surfactant/alcohol combination that shifts with the solubility of the surfactant qualitatively the same way as does the optimal salinity: but the CEC was found independent of the polymer type, polymer concentration (between the 100- and 1,000-ppm limits investigated), and surfactant concentration. The CEC increases with increasing temperature for the anionic surfactants and decreases with increasing temperature for the nonionic surfactants. When oil was added to the mixtures, an entirely different pattern of phase behavior was observed. As salinity increases, the particular formulations form the typical sequence of lower-phase microemulsion and excess oil, middle-phase microemulsion. excess oil, and excess brine: and upper-phase microemulsion and excess brine. The sequence with polymer was precisely the same over most of the salinity range but deviated over a limited range of salinity; the three-phase region simply shifted a small distance to the left on the salinity scale. Also, and probably more significantly, some of the aqueous phases in the critical region of the shift (which is also just above oil-free CEC salinity) were found to be gel-like in nature. These apparently occur under conditions such that the polymer concentration in the excess brine of the three-phase systems becomes very high because almost all the polymer is always in the brine phase, even when the brine phase is very small. Thus an overall 1,000 ppm of polymer easily can be concentrated to 10,000 ppm or more. One of the most remarkable aspects of the phase behavior of the surfactant/polymer systems is that the same patterns are observed for all combinations of anionic and nonionic surfactants and polymers. Also, little difference was observed in the IFT values with and without polymer. The three-phase systems still exhibited ultralow IFT values. Obviously, significant differences did occur in the brine viscosities when polymer was added. The polymer-free mixtures were themselves quite viscous, however, and the viscosity of the oil-free surfactant-rich phases (above the CEC) was significantly higher when the phases were in equilibrium with a polymer-rich aqueous phase, even though they apparently contained almost no polymer. We found that the polymer-rich phases had normal viscosities, as judged by the same polymer in the same brine at the expected concentration, assuming all the polymer was in the polymer-rich phase. The effect of polymer on the systems with oil was to increase the viscosity of the water-rich phase only, with little effect on the microemulsion phase unless it was the water-rich phase. SPEJ P. 816^

A Modified HLD-NAC Equation of State To Predict Alkali/Surfactant/Oil/Brine Phase Behavior

SPE Journal ◽  
2018 ◽  
Vol 23 (02) ◽  
pp. 550-566 ◽  
Author(s):  
Soumyadeep Ghosh ◽  
Russell T. Johns
Keyword(s):  
Equation Of State ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Naphthenic Acids ◽  
Phase Region ◽  
Measured Data ◽  
Synthetic Surfactant ◽  
Chemical Flooding ◽  
Mineral Surfaces ◽  
Dimensionless Equation

Summary Reservoir crudes often contain acidic components (primarily naphthenic acids), which undergo neutralization to form soaps in the presence of alkali. The generated soaps perform synergistically with injected synthetic surfactants to mobilize waterflood residual oil in what is termed alkali/surfactant/polymer (ASP) flooding. The two main advantages of using alkali in enhanced oil recovery (EOR) are to lower cost by injecting a lesser amount of expensive synthetic surfactant and to reduce adsorption of the surfactant on the mineral surfaces. The addition of alkali, however, complicates the measurement and prediction of the microemulsion phase behavior that forms with acidic crudes. For a robust chemical-flood design, a comprehensive understanding of the microemulsion phase behavior in such processes is critical. Chemical-flooding simulators currently use Hand's method to fit a limited amount of measured data, but that approach likely does not adequately predict the phase behavior outside the range of the measured data. In this paper, we present a novel and practical alternative. In this paper, we extend a dimensionless equation of state (EOS) (Ghosh and Johns 2016b) to model ASP phase behavior for potential use in reservoir simulators. We use an empirical equation to calculate the acid-distribution coefficient from the molecular structure of the soap. Key phase-behavior parameters such as optimum salinities and optimum solubilization ratios are calculated from soap-mole-fraction-weighted equations. The model is tuned to data from phase-behavior experiments with real crudes to demonstrate the procedure. We also examine the ability of the new model to predict fish plots and activity charts that show the evolution of the three-phase region. The predictions of the model are in good agreement with measured data.

Evaluation of the Salinity Gradient Concept in Surfactant Flooding

1983 ◽  
Vol 23 (03) ◽  
pp. 486-500 ◽  
Author(s):  
G.J. Hirasaki ◽  
H.R. van Domselaar ◽  
R.C. Nelson
Keyword(s):  
Active Region ◽  
Phase Behavior ◽  
Aqueous Phase ◽  
Surfactant Concentration ◽  
High Salinity ◽  
Salinity Gradient ◽  
Type Ii ◽  
Middle Phase ◽  
Optimal Salinity ◽  
Type Iii

Abstract Salinity design goals are to keep as much surfactant as possible in the active region and to minimize surfactant possible in the active region and to minimize surfactant retention. Achieving these is complicated becausecompositions change as a result of dispersion, chromatographic separation of components distributed among two or more phases, and retention by adsorption onto rock and/or absorption in a trapped phase-.in the presence of divalent ions, optimal salinity is not constant but a function of surfactant concentration and calcium/sodium ratio: andthe changing composition of a system strongly influences transport of the components. A one-dimensional (ID) six-component finite-difference simulator was used to compare a salinity gradient design with a constant salinity design. Numerical dispersion was used to evaluate the effects of dispersive mixing. These simulations show that, with a salinity gradient, change of phase behavior with salinity can be used to advantage both to keep surfactant in the active region and to minimize retention. By contrast, under some conditions with a constant salinity design. it is possible to have early surfactant breakthrough and/or large surfactant retention. Other experiments conducted showed that high salinity does retard surfactant, and, if the drive has high salinity. a great amount of surfactant retention can result. The design that produced the best recovery had the water flood brine over optimum and the drive under optimum; the peak surfactant concentration occurred in the active region and oil production ceased at the same point. Introduction The phase behavior of surfactant/oil/brine systems for different salinities is shown in Fig. 1. Low salinities. called "underoptimum" or "Type II(−)" phase behavior, are shown at the top of Fig. 1. In this kind of system, surfactant is partitioned predominantly into the aqueous phase. predominantly into the aqueous phase. High salinities, called "overoptimum" or "Type II(+)" phase behavior, are shown at the bottom of Fig. 1. In this kind of system, surfactant is partitioned predominantly into the oleic phase. When the oleic phase predominantly into the oleic phase. When the oleic phase has a low oil concentration, the oil is said to be "swollen" by the surfactant and brine. At moderate salinities, the system can have up to three phases and is called "Type III." This is illustrated in the phases and is called "Type III." This is illustrated in the middle of Fig. 1. The salinity at which the middle phase has a WOR of unity is called "optimal salinity" because the lowest interfacial tensions (IFT's) usually occur near this salinity. As salinity increases, there is a steady progression from Type II(−) to Type III to Type II(+) phase behavior. The middle-phase composition moves from the brine side of the diagram to the oil side. The two-phase regions that correspond to the Type II(−) and Type II( +) systems can be seen above the three-phase region in Fig. 1.

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