Application of the Theory of Multicomponent, Multiphase Displacement to Three-Component, Two-Phase Surfactant Flooding

1981 ◽  
Vol 21 (02) ◽  
pp. 191-204 ◽  
Author(s):  
George J. Hirasaki

Abstract The theory presented in a companion paper is illustrated for the case of three-component, two-phase (i.e., constant-salinity) surfactant flooding. The utility of this method is that, in addition to computation of specific cases, it provides a general qualitative understanding of the displacement behavior for different phase diagrams and different injection compositions. The phase behavior can be classified as to whether the partition coefficient is less than or greater than unity. The injection composition of the slug can be classified as to whether it is aqueous or oleic and whether it is inside or outside the region of tieline extensions.The theory provides an understanding of the displacement mechanisms for the three-component, two-phase system as a function of phase behavior and injection composition. This understanding aids the interpretation of phenomena such as the effects of dispersion, salinity gradient, chromatographic separation, and polymer/surfactant interaction. Introduction The phase behavior of surfactant with oil and brine is the underlying phenomenon of most surfactant-flood design philosophies. The surfactant slugs have been formulated either as (1) surfactant in water, (2) surfactant in oil, or (3) microemulsions containing both water and oil. Recovery of oil is thought to occur by solubilization, oil swelling, miscible displacement, and/or low interfacial tensions. The low interfacial tensions occur in a salinity environment such that three phases can coexist. At higher salinities the surfactant is in the oleic phase, and at lower salinities it is in the aqueous phase.Some recent investigators have preferred designing their process at a constant salinity even though their experiments indicated better oil recovery with a salinity contrast. Glover et al. point out that the optimal salinity is not constant in brines containing divalent ions and that phase trapping can result in large retention of surfactant in a system that was at optimal salinity at injected conditions. Nelson and Pope have demonstrated that good oil recovery is possible in systems containing formation brine with 120,000 ppm TDS and 3,000 ppm divalent cations if the drive salinity is sufficiently low such that the surfactant partitions into the aqueous phase. Moreover, the peak surfactant concentration in the effluent occurred in the three-phase environment where the lowest interfacial tension usually occurs.The purpose of this work is to understand better the mechanism of multiphase, multicomponent displacement so that the phase behavior can be used to advantage. The approach used is to examine in detail the displacement mechanism and behavior of a two-phase, three-component system. This understanding will build a foundation for examining more complex systems.Earlier, Larson and Hirasaki showed effects of oil swelling and the retardation of the surfactant front due to the surfactant partitioning into the oleic phase. Recently, Larson extended the work to finite slugs including oleic slugs. He showed the conditions necessary to have miscible or piston-like displacement. His work showed that systems with large partition coefficients are more tolerant to dispersive mixing. We show in this paper that his observation was probably the consequence of having a phase diagram with a constant partition coefficient. Todd et al. show the effect of the partition coefficients on the chromatographic separation and retention for a two-component surfactant system. Pope et al. evaluated the sensitivity of the performance of a surfactant flood to a number of factors. SPEJ P. 191^

1985 ◽  
Vol 50 (8) ◽  
pp. 1642-1647 ◽  
Author(s):  
Štefan Baláž ◽  
Anton Kuchár ◽  
Ernest Šturdík ◽  
Michal Rosenberg ◽  
Ladislav Štibrányi ◽  
...  

The distribution kinetics of 35 2-furylethylene derivatives in two-phase system 1-octanol-water was investigated. The transport rate parameters in direction water-1-octanol (l1) and backwards (l2) are partition coefficient P = l1/l2 dependent according to equations l1 = logP - log(βP + 1) + const., l2 = -log(βP + 1) + const., const. = -5.600, β = 0.261. Importance of this finding for assesment of distribution of compounds under investigation in biosystems and also the suitability of the presented method for determination of partition coefficients are discussed.


1976 ◽  
Vol 16 (03) ◽  
pp. 147-160 ◽  
Author(s):  
R.N. Healy ◽  
R.L. Reed ◽  
D.G. Stenmark

Abstract Economical microemulsion flooding inevitably involves microemulsion phases immiscible with oil or water, or both; oil recovery is largely affected by displacement efficiency during the immiscible regime. Therefore, it is essential to understand the role of interfacial tension in relation to multiphase microemulsion behavior. Three basic types of multiphase systems are identified and used to label phase transitions that occur when changes are made in salinity, temperature, oil composition, surfactant structure, cosolvent, and dissolved solids in the aqueous phase. Directional effects of these changes on phase behavior, interfacial tension, and solubilization parameter are tabulated for the alkyl aryl sufonates studied. A relationship between interfacial tension and phase behavior is established. This provides the phase behavior is established. This provides the basis for a convenient method for preliminary screening of surfactants for oil recovery. Interfacial tensions were found to correlate with the solubilization parameter for the various microemulsion phases, a result that can substantially reduce the number of interfacial tensions that must be determined experimentally for a given application. Introduction A previous paper established that microemulsion flooding is a locally miscible process until slug breakdown and is an immiscible, rate-dependent displacement thereafter; furthermore, for an effective flood, most of the oil recovered is acquired during the immiscible regime. An extensive study of single-phase regions defined classes of micellar structures for a particular surfactant; however, it was subsequently shown these did not affect oil recovery, provided viscous, lamellar structures were avoided. Optimal salinity was introduced as defining a ternary diagram having the least extensive multiphase region, a desirable feature in that locally miscible displacement is prolonged. Immiscible displacement after slug breakdown is known to depend on interfacial tension through its inclusion in the capillary number. A brief study showed chat interfacial tension varied widely throughout the multiphase region; accordingly, it is anticipated that oil recovery will depend on details of multiphase behavior in relation to interfacial tension, as well as on injection composition. Consider a flood sufficiently advanced that the microemulsion slug has broken down. A microemulsion phase remains that is immiscible with water or oil, phase remains that is immiscible with water or oil, or both, and displacement has assumed an immiscible character. The problem is twofold: to design a microemulsion slug that effectively displaces oil at the front and that is effectively displaced by water at the back. Both aspects are essential and, therefore, both microemulsion-oil and microemulsion-water interfacial tensions must be very low. The condition where these two tensions are low and equal will be of particular significance. The purpose of this paper is to explore physicochemical properties of multiphase physicochemical properties of multiphase microemulsion systems with a view toward understanding immiscible aspects of microemulsion flooding, and with the expectation of developing systematic screening procedures useful for design of optimal floods. Equilibration is an essential part of this study. Even the simplest of these systems is so complex it may well happen that nonequilibrium effects will never be understood sufficiently to be usefully accommodated in mathematical simulation of microemulsion flooding. In any event, equilibration, although time consuming, leads to a coherent picture of multiphase behavior that can be correlated with flooding results. Multiphase behavior of "simple" ternary systems divides into three basic classes. Dependence of phase behavior on salinity, with respect to these phase behavior on salinity, with respect to these classes, leads to correlations of interfacial tension with the solubilization parameter. These correlations are studied in relation to surfactant structure, temperature, cosolvents, oil composition, and brine composition. Optimal salinity again plays an important role, especially in relation to interfacial tension. SPEJ P. 147


1977 ◽  
Vol 17 (03) ◽  
pp. 193-200 ◽  
Author(s):  
M.C. Puerto ◽  
W.W. Gale

Abstract Economic constraints are such that it is unlikely a pure surfactant will be used for major enhanced oil recovery projects. However, it is possible to manufacture at competitive prices classes of syntheic and natural petroleum sulfonates that have fairly narrow molecular-weight distributions. Under some reservoir conditions, one of these narrow-distribution sulfonates may serve quite well as the basic component of a surfactant flood, however, in many instances a mixture of two or more of these may be required. Since evaluation of a significant subset of "all possible combinations" is a formidable undertaking screening techniques must be established that can reduce the number of laboratory core floods required. It is well known that interfacial tension plays a dominant role in surfactant flooding. It has recently been shown that minimal interfacial tensions occur at optimal salinity, Cphi, where the solubilization parameters VO/Vs and Vw/Vs are equal. Additionally, it has been shown that interracial tensions are inversely proportional to the magnitude of the solubilization parameters. This paper demonstrates that optimal salinity and solubilization parameters for any mixture of orthoxylene sulfonates can be estimated by summation of mole-fraction-weighted component properties. Those properties, which could not be properties. Those properties, which could not be measured directly, were obtained by least-squares regression on mixture data. Moreover, for surfactants of known carbon number distributions, equations that are linear in mole fractions of components and logarithmic in alkyl carbon number were found to be excellent estimators of both Cphi and solubilization parameters evaluated at Cphi. parameters evaluated at Cphi. Optimal salinity and associated solubilization parameters were measured using constant weight parameters were measured using constant weight fractions of alcohol cosolvents and mixtures of seven products with narrow molecular weight distributions. The average alkyl carbon number of these products varied from about 8 to 19. Alkyl chain lengths of individual surfactant chemical species ranged from 6 to 24 carbon atoms. Introduction Optimal salinity and the amounts of oil and water contained in a microemulsion have been shown to play important roles in obtaining low interfacial tensions and high oil recoveries. Since economics of enhanced oil recovery projects demand use of inexpensive surfactants, broad-distribution products likely will be chosen. Knowledge of how to estimate optimal salinity and oil-water contents of microemulsions prepared from such products would reduce time involved in laboratory screening procedures. This paper presents a method for procedures. This paper presents a method for obtaining such estimates that should prove useful for all types of surfactant mixtures that involve homologous series. The basic concept used is that a given property of a mixture of components (Yi) is related to the sum of products of mole fraction of components in the mixture (Xij) and the "mixing value" of the property in question for that component (Y'j). In property in question for that component (Y'j). In other words, (1) This approach is similar, for example, to the pseudocritical method used by Kay to calculate pseudocritical method used by Kay to calculate gas deviation factors at high pressures. The properties of interest in this paper are optimal properties of interest in this paper are optimal salinity and solubilization parameters, Vo/Vs, and Vw/Vs, at optimal salinity. Two separate approaches were developed that depended on the degree of detail of the available surfactant-composition data. In the first approach, only average molecular weights of several surfactant products were assumed known. Optimal salinity and products were assumed known. Optimal salinity and solubilization parameters could be measured for some, but not all, of the products. Regression on mixture data was used to estimate these quantities for the remainder of the products. Those properties, either measured experimentally or estimated from mixture data, are referred to as surfactant product contributions since they can be used as mixing values of the property in question in Eq. 1 or Eq. 2. SPEJ P. 193


1984 ◽  
Vol 24 (06) ◽  
pp. 606-616 ◽  
Author(s):  
Charles P. Thomas ◽  
Paul D. Fleming ◽  
William K. Winter

Abstract A mathematical model describing one-dimensional (1D), isothermal flow of a ternary, two-phase surfactant system in isotropic porous media is presented along with numerical solutions of special cases. These solutions exhibit oil recovery profiles similar to those observed in laboratory tests of oil displacement by surfactant systems in cores. The model includes the effects of surfactant transfer between aqueous and hydrocarbon phases and both reversible and irreversible surfactant adsorption by the porous medium. The effects of capillary pressure and diffusion are ignored, however. The model is based on relative permeability concepts and employs a family of relative permeability curves that incorporate the effects of surfactant concentration on interfacial tension (IFT), the viscosity of the phases, and the volumetric flow rate. A numerical procedure was developed that results in two finite difference equations that are accurate to second order in the timestep size and first order in the spacestep size and allows explicit calculation of phase saturations and surfactant concentrations as a function of space and time variables. Numerical dispersion (truncation error) present in the two equations tends to mimic the neglected present in the two equations tends to mimic the neglected effects of capillary pressure and diffusion. The effective diffusion constants associated with this effect are proportional to the spacestep size. proportional to the spacestep size. Introduction In a previous paper we presented a system of differential equations that can be used to model oil recovery by chemical flooding. The general system allows for an arbitrary number of components as well as an arbitrary number of phases in an isothermal system. For a binary, two-phase system, the equations reduced to those of the Buckley-Leverett theory under the usual assumptions of incompressibility and each phase containing only a single component, as well as in the more general case where both phases have significant concentrations of both components, but the phases are incompressible and the concentration in one phase is a very weak function of the pressure of the other phase at a given temperature. pressure of the other phase at a given temperature. For a ternary, two-phase system a set of three differential equations was obtained. These equations are applicable to chemical flooding with surfactant, polymer, etc. In this paper, we present a numerical solution to these equations paper, we present a numerical solution to these equations for I D flow in the absence of gravity. Our purpose is to develop a model that includes the physical phenomena influencing oil displacement by surfactant systems and bridges the gap between laboratory displacement tests and reservoir simulation. It also should be of value in defining experiments to elucidate the mechanisms involved in oil displacement by surfactant systems and ultimately reduce the number of experiments necessary to optimize a given surfactant system.


1981 ◽  
Vol 21 (01) ◽  
pp. 63-76 ◽  
Author(s):  
Paul D. Fleming ◽  
Charles P. Thomas ◽  
William K. Winter

Abstract A general multiphase, multicomponent chemical flood model has been formulated. The set of mass conservation laws for each component in an isothermal system is closed by assuming local thermodynamic (phase) equilibrium, Darcy's law for multiphase flow through porous media, and Fick's law of diffusion. For the special case of binary, two-phase flow of nonmixing incompressible fluids, the equations reduce to those of Buckley and Leverett. The Buckley-Leverett equations also may be obtained for significant fractions of both components in the phases if the two phases are sufficiently incompressible. To illustrate the usefulness of the approach, a simple chemical flood model for a ternary, two-phase system is obtained which can be applied to surfactant flooding, polymer flooding, caustic flooding, etc. Introduction Field tests of various forms of surfactant flooding currently are under way or planned at a number of locations throughout the country.1 The chemical systems used have become quite complicated, often containing up to six components (water, oil, surfactant, alcohol, salt, and polymer). The interactions of these components with each other and with the reservoir rock and fluids are complex and have been the subject of many laboratory investigations.2–22 To aid in organizing and understanding laboratory work, as well as providing a means of extrapolating laboratory results to field situations, a mathematical description of the process is needed. Although it seems certain that mathematical simulations of such processes are being performed, models aimed specifically at the process have been reported only recently in the literature.23–31 It is likely that many such simulations are being performed on variants of immiscible, miscible, and compositional models that do not account for all the facets of a micellar/polymer process. To help put the many factors of such a process in proper perspective, a generalized model has been formulated incorporating an arbitrary number of components and an arbitrary number of phases. The development assumes isothermal conditions and local phase equilibrium. Darcy's law32,33 is assumed to apply to the flow of separate phases, and Fick's law34 of diffusion is applied to components within a phase. The general development also provides for mass transfer of all components between phases, the adsorption of components by the porous medium, compressibility, gravity segregation effects, and pressure differences between phases. With the proper simplifying assumptions, the general model is shown to degenerate into more familiar special cases. Numerical solutions of special cases of interest are presented elsewhere.35


SPE Journal ◽  
2008 ◽  
Vol 13 (01) ◽  
pp. 5-16 ◽  
Author(s):  
Shunhua Liu ◽  
Danhua Zhang ◽  
Wei Yan ◽  
Maura Puerto ◽  
George J. Hirasaki ◽  
...  

Summary A laboratory study of the alkaline-surfactant-polymer (ASP) process was conducted. It was found from phase-behavior studies that for a given synthetic surfactant and crude oil containing naphthenic acids, optimal salinity depends only on the ratio of the moles of soap formed from the acids to the moles of synthetic surfactant present. Adsorption of anionic surfactants on carbonate surfaces is reduced substantially by sodium carbonate, but not by sodium hydroxide. The magnitude of the reduction with sodium carbonate decreases with increasing salinity. Particular attention was given to a surfactant blend of a propoxylated sulfate having a slightly branched C16-17 hydrocarbon chain and an internal olefin sulfonate. In contrast to alkyl/aryl sulfonates previously considered for EOR, alkaline solutions of this blend containing neither alcohol nor oil were single-phase micellar solutions at all salinities up to approximately optimal salinity with representative oils. Phase behavior with a west Texas crude oil at ambient temperature in the absence of alcohol was unusual in that colloidal material, perhaps another microemulsion having a higher soap content, was dispersed in the lower-phase microemulsion. Low interfacial tensions existed with the excess oil phase only when this material was present in sufficient amount in the spinning-drop device. Some birefringence was observed near and above optimal conditions. While this phase behavior is somewhat different from the conventional Winsor phase sequence, overall solubilization of oil and brine for this system was high, leading to low interfacial tensions over a wide salinity range and to excellent oil recovery in both dolomite and silica sandpacks. The sandpack experiments were performed with surfactant concentrations as low as 0.2 wt% and at a salinity well below optimal for the injected surfactant. It was necessary that sufficient polymer be present to provide adequate mobility control, and that salinity be below the value at which phase separation occurred in the polymer/surfactant solution. A 1D simulator was developed to model the process. By calculating transport of soap formed from the crude oil and injected surfactant separately, it showed that injection below optimal salinity was successful because a gradient in local soap-to-surfactant ratio developed during the process. This gradient increases robustness of the process in a manner similar to that of a salinity gradient in a conventional surfactant process. Predictions of the simulator were in excellent agreement with the sandpack results. Background Although both injection of surfactants and injection of alkaline solutions to convert naturally occurring naphthenic acids in crude oils to soaps have long been suggested as methods to increase oil recovery, key concepts such as the need to achieve ultralow interfacial tensions and the means for doing so using microemulsions were not clarified until a period of intensive research between approximately 1960 and 1985 (Reed and Healy 1977; Miller and Qutubuddin 1987; Lake 1989). Most of the work during that period was directed toward developing micellar-polymer processes to recover residual oil from sandstone formations using anionic surfactants. However, Nelson et al. (1984) recognized that in most cases the soaps formed by injecting alkali would not be at the "optimal" conditions needed to achieve low tensions. They proposed that a relatively small amount of a suitable surfactant be injected with the alkali so that the surfactant/soap mixture would be optimal at reservoir conditions. With polymer added for mobility control, the process would be an alkaline-surfactant-polymer (ASP) flood. The use of alkali also reduces adsorption of anionic surfactants on sandstones because the high pH reverses the charge of the positively charged clay sites where adsorption occurs. The initial portion of a Shell field test, which did not use polymer, demonstated that residual oil could be displaced by an alkaline-surfactant process (Falls et al. 1994). Several ASP field projects have been conducted with some success in recent years in the US (Vargo et al. 2000; Wyatt et al. 2002). Pilot ASP tests in China have recovered more than 20% OOIP in some cases, but the process has not yet been applied there on a large scale (Chang et al. 2006).


2018 ◽  
Vol 7 (4.30) ◽  
pp. 377
Author(s):  
Zatul Iffah Mohd Arshad ◽  
Azura Amid

Recombinant bromelain is a protease that was partially purified using aqueous two-phase system (ATPS). The process variables (pH, PEG 6000 and potassium phosphate concentration) were optimized on enzyme activity and partition coefficient using response surface methodology (RSM) based on a face-centered central composite design (FCCCD) model. The optimum conditions for purification were at 18.47% [w/w] PEG6000 and 13% [w/w] potassium phosphate, pH 7.0 with enzyme activity was obtained as 0.272±0.0036 unit m/L, and partition coefficient as 1.394±0.093. The recombinant bromelain was preferentially partitioned into the top phase and the band was reduced in contrast to crude sample on SDS-PAGE gel.


1951 ◽  
Vol 35 (1) ◽  
pp. 55-65 ◽  
Author(s):  
V. G. Dethier

Rejection thresholds of eight primary alcohols applied to the tarsal chemoreceptors of the blowfly Phormia regina Meigen and the ovipositor of Gryllus assimilis Fab. have been determined. Three different solvents for the alcohols have been used: water, ethylene glycol, and mineral oil. The comparative stimulating effectiveness of the alcohols assumes a different aspect with each different solvent. In oil the range of thresholds from methanol to octanol extends over less than one log unit as compared with the corresponding thresholds in water which extend over four log units. In glycol the thresholds extend over two and one half log units only. When water is employed as a solvent, the line which describes the relationship between threshold concentration and chain length of the compound exhibits a sharp break at or near butanol. No such discontinuity is evident when glycol or oil is employed as solvent. This is offered as evidence supporting the hypothesis that the limiting mechanism in tarsal chemoreception involves a two phase system whereby highly water-soluble compounds gain access to the receptor through an aqueous phase and the larger lipoid-soluble molecules chiefly through a lipoid phase. Additional facts which support this idea are gained from data which show that the inflection in the curve occurs at different points with different species of insects and is conspicuously absent in the case of man. When thresholds in aqueous solutions are converted from molar concentrations to activities, it is clear that the relation of equal physiological effect at equal thermodynamic activities does not apply here. The lower members of the series stimulate at progressively increasing activities up to pentanol and then at progressively decreasing activities. Furthermore, the ratio of water threshold to oil threshold exhibits no obvious agreement with the water/oil partition coefficients determined experimentally. These results indicate either that the limiting process of chemoreception in these insects does not depend upon the establishment of an equilibrium or that some kinetic effect is obscuring an underlying relationship which does so depend.


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