Modeling of Pressure and Solution Gas for Chemical Floods

SPE Journal ◽  
2013 ◽  
Vol 18 (03) ◽  
pp. 428-439 ◽  
Author(s):  
M.. Roshanfekr ◽  
R.T.. T. Johns ◽  
M.. Delshad ◽  
G.A.. A. Pope
Keyword(s):  
Phase Behavior ◽  
Oil Recovery ◽  
Atmospheric Pressure ◽  
Carbon Number ◽  
Chemical Flooding ◽  
Reservoir Pressure ◽  
Optimal Salinity ◽  
Free Gas ◽  
Cubic Equation ◽  
Solution Gas

Summary The goal of surfactant/polymer (SP) flooding is to reduce interfacial tension (IFT) between oil and water so that residual oil is mobilized and high recovery is achieved. The optimal salinity and optimal solubilization ratios that correspond to ultralow IFT have recently been shown, in some cases, to be a strong function of the methane mole fraction in the oil at reservoir pressure. We incorporate a recently developed methodology to determine the optimal salinity and solubilization ratio at reservoir pressure into a chemical-flooding simulator (UTCHEM). The proposed method determines the optimal conditions on the basis of density estimates by use of a cubic equation of state (EOS) and measured phase-behavior data at atmospheric pressure. The microemulsion phase-behavior (Winsor I, II, and III) are adjusted on the basis of this predicted optimal salinity and solubilization ratio in the simulator. Parameters for the surfactant phase-behavior equation are modified to account for these changes, and the trend in the equivalent alkane carbon number (EACN) is automatically adjusted for pressure and methane content in each simulation gridblock. We use phase-behavior data from several potential SP floods to demonstrate the new implementation. The implementation of the new phase-behavior model into a chemical-flooding simulator allows for a better design of SP floods and more-accurate estimations of oil recovery. The new approach could also be used to handle free gas that may form in the reservoir; however, the SP-flood simulation when free gas is present is not the focus of this paper. We show that not accounting for the phase-behavior changes that occur when methane is present at reservoir pressure can greatly affect the oil recovery of SP floods. Improper design of an SP flood can lead to production of more oil as a microemulsion phase than as an oil bank. This paper describes the procedure to implement the effect of pressure and solution gas on microemulsion phase behavior in a chemical-flooding simulator, which requires the phase-behavior data measured at atmospheric pressure.

Simulation of Surfactant/Polymer Floods With a Predictive and Robust Microemulsion Flash Calculation

SPE Journal ◽  
2016 ◽  
Vol 22 (02) ◽  
pp. 470-479 ◽  
Author(s):  
Saeid Khorsandi ◽  
Changhe Qiao ◽  
Russell T. Johns
Keyword(s):  
Experimental Data ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Carbon Number ◽  
General Purpose ◽  
Accurate Estimation ◽  
Chemical Flooding ◽  
Two Phase ◽  
Data Set ◽  
Average Curvature

Summary A compositional reservoir simulator that uses a predictive microemulsion phase-behavior model is essential for accurate estimation of oil recovery from surfactant/polymer (SP) floods. Current chemical-flooding simulators, however, use Hand's model (Hand 1939) for phase-behavior calculation. Hand's model can reasonably fit a limited set of experimental data, such as those of a salinity scan, but because it is empirical, it cannot predict phase behavior outside the matched data set. Hydrophyllic/lypophyllic difference (HLD) and net-average-curvature (NAC) equation of state (EOS) (Acosta et al. 2003) has shown great performance for tuning and prediction of experimental data. In this paper, the EOS model with the extension to two-phase regions has been incorporated for the first time into UTCHEM (2000) and our in-house general-purpose compositional simulator, PennSim (2013). All Winsor regions (Type II−, II+, III, and IV) are modeled by use of a consistent physics-based EOS model without the need for Hand's approach. The new simulator is therefore able to account correctly for gridblock properties, which can vary temporally and spatially, and significantly improve the modeling of phase behavior and oil recovery. The results show excellent agreement between UTCHEM and PennSim both in composition space and for composition/saturation profiles for the 1D simulation. The effects of varying pressure, temperature, equivalent alkane carbon number (EACN), and salinity on recoveries are demonstrated also in 1D simulations.

An Equation-of-State Model To Predict Surfactant/Oil/Brine-Phase Behavior

SPE Journal ◽  
2016 ◽  
Vol 21 (04) ◽  
pp. 1106-1125 ◽  
Author(s):  
S.. Ghosh ◽  
R. T. Johns
Keyword(s):  
Experimental Data ◽  
Equation Of State ◽  
Phase Behavior ◽  
Oil Recovery ◽  
Atmospheric Pressure ◽  
Carbon Number ◽  
Oil Reservoirs ◽  
Potential Candidate ◽  
Average Curvature ◽  
Formulation Variables

Summary Surfactant/polymer (SP) floods have significant potential to recover waterflood residual oil in shallow oil reservoirs. A thorough understanding of surfactant/oil/brine-phase behavior is critical to design SP-flood processes. Current practices involve repetitive laboratory experiments of dead crude at atmospheric pressure in a salinity scan that aims at finding an “optimum formulation” of chemicals for targeted oil reservoirs. Although considerable progress has been made in developing surfactants and polymers that increase the potential of a chemical enhanced-oil-recovery (EOR) project, very little progress has been made to predict phase behavior as a function of formulation variables such as pressure, temperature, and oil equivalent alkane carbon number (EACN). The empirical Hand (1930) plot is still used today to model the microemulsion-phase behavior with little predictive capability because these and other formulation variables change. Such models could lead to incorrect recovery predictions and improper SP-flood designs. In this research, we develop a new predictive-phase-behavior model and introduce a new factor β to account for pressure changes in the HLD equation. This new HLD equation is coupled with the net-average-curvature (NAC) model to predict phase volumes, solubilization ratios, and microemulsion-phase transitions (Winsor II–, Winsor III, and Winsor II+). The predictions of key parameters are compared with experimental data and are within relative errors of 4% (average 2.35%) for measured optimum salinities and 17% (average 10.55%) for optimum solubilization ratios. This paper is the first to use the HLD/NAC model to predict microemulsion-phase behavior for live crudes, including optimal solubilization ratio and the salinity width of the three-phase Winsor III region at different temperatures and pressures. Although the effect of pressure variations on microemulsion-phase behavior is generally thought to be small compared with temperature-induced changes, we show here that this is not necessarily the case. The predictive approach relies on tuning the model to limited experimental data (such as at atmospheric pressure) similar to what is performed for equation-of-state (EOS) modeling of miscible gasfloods. This new EOS-like model could significantly aid the design of chemical floods where key variables change dynamically, and in screening of potential candidate reservoirs for chemical EOR.

Estimation of Optimal Salinity and Solubilization Parameters for Alkylorthoxylene Sulfonate Mixtures

1977 ◽  
Vol 17 (03) ◽  
pp. 193-200 ◽  
Author(s):  
M.C. Puerto ◽  
W.W. Gale
Keyword(s):  
Molecular Weight ◽  
Enhanced Oil Recovery ◽  
Mole Fraction ◽  
Oil Recovery ◽  
Carbon Number ◽  
Constant Weight ◽  
Optimal Salinity ◽  
Interfacial Tensions ◽  
Molecular Weight Distributions ◽  
Weight Distributions

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

Development of the Surfactant-Based Chemical EOR Formula for Low Permeability Reservoirs

2021 ◽  
Author(s):  
Nancy Chun Zhou ◽  
Meng Lu ◽  
Fuchen Liu ◽  
Wenhong Li ◽  
Jianshen Li ◽  
...  
Keyword(s):  
Phase Behavior ◽  
Oil Recovery ◽  
Aqueous Solubility ◽  
Low Permeability ◽  
Chemical Flooding ◽  
Residual Oil ◽  
Key Factors ◽  
Low Salinity ◽  
Low Tension ◽  
Low Permeability Reservoirs

Abstract Based on the results of the foam flooding for our low permeability reservoirs, we have explored the possibility of using low interfacial tension (IFT) surfactants to improve oil recovery. The objective of this work is to develop a robust low-tension surfactant formula through lab experiments to investigate several key factors for surfactant-based chemical flooding. Microemulsion phase behavior and aqueous solubility experiments at reservoir temperature were performed to develop the surfactant formula. After reviewing surfactant processes in literature and evaluating over 200 formulas using commercially available surfactants, we found that we may have long ignored the challenges of achieving aqueous stability and optimal microemulsion phase behavior for surfactant formulations in low salinity environments. A surfactant formula with a low IFT does not always result in a good microemulsion phase behavior. Therefore, a novel synergistic blend with two surfactants in the formulation was developed with a cost-effective nonionic surfactant. The formula exhibits an increased aqueous solubility, a lower optimum salinity, and an ultra-low IFT in the range of 10-4 mN/m. There were challenges of using a spinning drop tensiometer to measure the IFT of the black crude oil and the injection water at reservoir conditions. We managed the process and studied the IFTs of formulas with good Winsor type III phase behavior results. Several microemulsion phase behavior test methods were investigated, and a practical and rapid test method is proposed to be used in the field under operational conditions. Reservoir core flooding experiments including SP (surfactant-polymer) and LTG (low-tension-gas) were conducted to evaluate the oil recovery. SP flooding with a selected polymer for mobility control and a co-solvent recovered 76% of the waterflood residual oil. Furthermore, 98% residual crude oil recovery was achieved by LTG flooding through using an additional foaming agent and nitrogen. These results demonstrate a favorable mobilization and displacement of the residual oil for low permeability reservoirs. In summary, microemulsion phase behavior and aqueous solubility tests were used to develop coreflood formulations for low salinity, low temperature conditions. The formulation achieved significant oil recovery for both SP flooding and LTG flooding. Key factors for the low-tension surfactant-based chemical flooding are good microemulsion phase behavior, a reasonably aqueous stability, and a decent low IFT.

Oil emulsion characteristics as significance in efficiency forecast of oil-displacing formulations based on surfactants

2021 ◽  
pp. 91-107
Author(s):  
E. A. Turnaeva ◽  
E. A. Sidorovskaya ◽  
D. S. Adakhovskij ◽  
E. V. Kikireva ◽  
N. Yu. Tret'yakov ◽  
...  
Keyword(s):  
Oil Recovery ◽  
Surfactant Concentration ◽  
Chemical Flooding ◽  
Optimal Salinity ◽  
Oil Emulsion ◽  
Oil Displacement ◽  
Laboratory Selection ◽  
Reservoir Conditions ◽  
Selection Of ◽  
Comprehensive Study

Enhanced oil recovery in mature fields can be implemented using chemical flooding with the addition of surfactants using surfactant-polymer (SP) or alkaline-surfactant-polymer (ASP) flooding. Chemical flooding design is implemented taking into account reservoir conditions and composition of reservoir fluids. The surfactant in the oil-displacing formulation allows changing the rock wettability, reducing the interfacial tension, increasing the capillary number, and forming an oil emulsion, which provides a significant increase in the efficiency of oil displacement. The article is devoted with a comprehensive study of the formed emulsion phase as a stage of laboratory selection of surfactant for SP or ASP composition. In this work, the influence of aqueous phase salinity level and the surfactant concentration in the displacing solution on the characteristics of the resulting emulsion was studied. It was shown that, according to the characteristics of the emulsion, it is possible to determine the area of optimal salinity and the range of surfactant concentrations that provide increased oil displacement. The data received show the possibility of predicting the area of effectiveness of ASP and SP formulations based on the characteristics of the resulting emulsion.

A Fully Implicit, Parallel, Compositional Chemical Flooding Simulator

SPE Journal ◽  
2007 ◽  
Vol 12 (03) ◽  
pp. 322-338 ◽  
Author(s):  
Choongyong Han ◽  
Mojdeh Delshad ◽  
Kamy Sepehrnoori ◽  
Gary Arnold Pope
Keyword(s):  
Equation Of State ◽  
Interfacial Tension ◽  
Phase Behavior ◽  
Hybrid Approach ◽  
Material Balance ◽  
Chemical Flooding ◽  
Balance Equations ◽  
Cubic Equation ◽  
Fully Implicit ◽  
Simulation Results

Summary A fully implicit, parallel, compositional reservoir simulator has been developed that includes both a cubic equation of state model for the hydrocarbon phase behavior and Hand's rule for the surfactant/oil/brine phase behavior. The aqueous species in the chemical model include surfactant, polymer, and salt. The physical property models include surfactant/oil/brine phase behavior, interfacial tension, viscosity, adsorption, and relative permeability as a function of trapping number. The fully implicit simulation results were validated by comparison with results from our IMPEC chemical flooding simulator (UTCHEM). The results indicate that the simulator scales well using clusters of workstations. Also, simulation results from parallel runs are identical to those using a single processor. Field-scale surfactant/polymer flood simulations were successfully performed with over 1,000,000 gridblocks using multiple processors. Introduction Chemical flooding is a method to improve oil recovery that involves the injection of a solution of surfactant and polymer followed by a polymer solution. The surfactant causes the mobilization of oil by decreasing interfacial tension, whereas the polymer increases the sweep efficiency by lowering the mobility ratio. Chemical flooding has the potential to recover a very high fraction of the remaining oil in a reservoir, but the process needs to be designed to be both cost effective and robust, which requires careful optimization. Several reservoir simulators with chemical flooding features have been developed as a tool for optimizing the design (Delshad et al. 1996; Schlumberger 2004; Computer Modeling 2004). The University of Texas chemical flooding simulator, UTCHEM (Delshad et al. 1996) is an example of a simulator that has been used for this purpose. However, because UTCHEM is an Implicit Pressure and Explicit Concentration (IMPEC) formulation and in its current form cannot run on parallel computers, realistic surfactant/polymer flooding simulations are limited to around 100,000 gridblocks because of small timestep restrictions and insufficient memory. Recently, the appropriate chemical module was added to the fully implicit, parallel, EOS compositional simulator called GPAS (General Purpose Adaptive Simulator) based on a hybrid approach (John et al. 2005). GPAS uses a cubic equation of state model for the hydrocarbon phase behavior and the parallel and object-based Fortran 95 framework for managing memory, input/output, and the necessary communication between processors (Wang et al. 1999; Parashar et al. 1997). In the hybrid approach implemented in GPAS, the material balance equations for hydrocarbon and water components are solved implicitly first. Then, the material balance equations for the aqueous components such as surfactant, polymer, and electrolytes are solved explicitly using the updated phase fluxes, saturations, and densities.

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.

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^

Ethoxylated Oleyl Sulfonates as Model Compounds for Enhanced Oil Recovery

1985 ◽  
Vol 25 (03) ◽  
pp. 351-357 ◽  
Author(s):  
Irene Carmona ◽  
R.S. Schecter ◽  
W.H. Wade ◽  
Upali Weerasooriya
Keyword(s):  
Ethylene Oxide ◽  
Oil Recovery ◽  
Surfactant Concentration ◽  
Elevated Temperatures ◽  
Carbon Number ◽  
Effect Of Temperature ◽  
Distilled Water ◽  
Optimal Salinity ◽  
Shorthand Notation ◽  
Pure Grade

Abstract Precisely ethoxylated oleyl sulfonates were prepared and Precisely ethoxylated oleyl sulfonates were prepared and studied as model surfactant candidates for EOR. They were found to yield low interfacial tensions (IFT's), to give high solubilization parameters, and to have high electrolyte tolerance. Unfortunately, as a class of compounds they have a tendency to form liquid crystals (rather than microemulsions), which must be overcome by adding cosolvents, elevating temperatures, or restricting the maximally ethoxylated species. Introduction The indispensable primary requirement for any surfactant to be considered as a possible candidate in EOR processes is its ability to form systems with ultra low IFT's processes is its ability to form systems with ultra low IFT's between immiscible phases. To this requirement others must be added: minimal alcohol concentrations, good electrolyte tolerance (especially including multivalent cations such as Ca + + and Mg + +), and maximal values of solubilization parameters. Many ethoxylated species that satisfy the required tolerance to electrolyte have been studied in this laboratory; however, the species investigated have not given IFT's or solubilization parameters of as good quality as those found for many sulfonates. The commercially available species similar to the ones reported here have several disadvantages:(1)they exist only as sulfates, and these species hydrolyze at elevated temperatures;(2)there is a Gaussian distribution of ethylene oxide numbers (EON), which causes partitioning complications; and(3)there is less than perfect partitioning complications; and(3)there is less than perfect knowledge of the structure of the hydrophobic tail. The purpose of this study is to remove these three purpose of this study is to remove these three complications through the use of a monoisomeric ethoxylated sulfonate species, in particular 1-oleyl sulfonate with 1, 2, or 3 moles of ethylene oxide (EO) added between the oleyl and sulfonate groups. The species were chosen for two additional reasons. First, earlier results on alkylbenzene sulfonates indicated that straight-tailed hydrophobes maximized the solubilization parameter, and second, there is little information available on the effect of the benzene rings in the molecule on its EOR properties. In our paper a shorthand notation will be used properties. In our paper a shorthand notation will be used for the structure C8H17-CH=CH-C8H 16-(OCH2CH2), SO3Na, where n = 1, 2, 3. The molecules will simply be referred to as n=l, n=2, n=3. Experimental Procedure The synthesis of the surfactant species is described elsewhere, but a brief description is given in the appendix. The various alkanes (pure grade from Phillips Petroleum Co.), singly distilled water, NaCl (Baker's Petroleum Co.), singly distilled water, NaCl (Baker's CP), and alcohol cosolvents (sec-butanol [SB] and isopentanol [IP]), were Baker's pure grade. Surfactant formulations were equilibrated in sealed 5-cm [5-mL] disposable pipettes. The surfactant concentration in all studies was pipettes. The surfactant concentration in all studies was 0.025 M and the SB concentration usually Was held constant. The tubes were equilibrated daily by shaking; after the third day, the various phase volumes were found to no longer change with time. All the solubilization parameters reported here are for optimal systems (equal water and oil solubilized) and were calculated assuming that all the surfactant, but none of the alcohol, was in the middle phase. Furthermore, in this study the concentrations of phase. Furthermore, in this study the concentrations of surfactant, NaCl, CaC12, and alcohol are based on the initial aqueous-phase volume, and the WOR was always one. As found earlier, optimal formulations had minimal phase equilibrium times; this often was used to identify such systems preliminarily. Results and Discussion Effect of Temperature on Phase Behavior. Two standard methods previously have been used to examine the effect of temperature on phase behavior:studying its effect on optimal salinity andstudying its effect on optimal alkane carbon number (ACN). We have chosen to do the latter. The alcohol concentration chosen for this study was sufficiently high to destroy any liquid crystal or surfactant aggregations over the entire ACN/ temperature range studied. SPEJ P. 351

Interpretation of the Change in Optimal Salinity With Overall Surfactant Concentration

1982 ◽  
Vol 22 (06) ◽  
pp. 971-982 ◽  
Author(s):  
George J. Hirasaki
Keyword(s):  
Sodium Chloride ◽  
Phase Behavior ◽  
Surfactant Concentration ◽  
Equilibrium Composition ◽  
Chemical Flooding ◽  
Alkyl Ether ◽  
Divalent Ions ◽  
Optimal Salinity ◽  
Phase Rule ◽  
Compositional Simulator

Abstract Background. For chemical flooding formulations, optimal salinity changes with overall surfactant concentration when the phase behavior is observed in test tubes. Applying these observations to the mathematical simulator is questionable because chromatographic mechanisms during displacement through porous media result in different compositions. Purpose. This work sought the mechanism for the observed change so that calculated optimal salinity can be expressed through the appropriate intensive variable rather than overall surfactant concentration. Method. Association of the alcohol has been described by partition coefficients for distribution of the alcohol among brine, oil, and surfactant. The alcohol was isopropanol (IPA), 1-butanol (NBA), or tertiary amyl alcohol (TAA) in the systems in which they were included and was used to represent a disulfonate in the system with Petrostep petroleum sulfonate. Association of sodium and divalent ions with surfactant has been described by the Donnan equilibrium model, which experimental observations show can be applied to microemulsions as well as to micelles. Conclusions. For the seven systems investigated, the change in optimal salinity is a function of (1) the alcohol associated with the surfactant and (2) the divalent ion fraction of the associated counterions. Introduction Reed and Healy reviewed the concept of optimal salinity for minimum inter-facial tension (IFT) and its relationship to phase behavior. They showed that, as a first approximation, phase behavior can be represented by electrolyte concentration and three pseudocomponents: brine, oil, and surfactant plus cosolvent. If the system actually contains three components plus sodium chloride, optimal salinity should be independent of overall surfactant concentration and WOR. However. in the system Reed and Healy investigated, optimal salinity changed with overall surfactant concentration and WOR, which indicates that the system did not contain just sodium chloride plus three additional components. To handle this problem, Vinatieri and Fleming suggested using regression analysis to determine the best set of pseudocomponents. Then alcohol can be included with the oil and brine as pseudocomponents. Blevins et al. examined the phase behavior of a quaternary system (with brine as a pseudocomponent) by examining pseudoternary planes on a quaternary diagram. Glover et al. showed that the change in optimal salinity of a system containing divalent ions can be modeled by (1) considering the equilibrium composition of the brine, and (2) describing optimal salinity as a linear function of the concentration of divalent ions associated with the sulfonate. They assumed that NEODOL 25-3S did not associate divalent ions. (NEODOL 25-3S is a sodium salt of C12-C15 alkyl ether sulfate, with an average ethylene oxide number of three. Hereafter in this paper it is abbreviated as N253S.) Pope and Nelson showed that phase behavior and IFT's can be modeled in a compositional simulator when optimal salinity and the upper and lower limits of the Type III environment are known. The purpose of this work is to model alcohol or multiple surfactant components and divalent ions so that they can be included in a compositional simulator. Thermodynamic Analysis The Gibbs phase rule is used to show that a four-component system of pure oil, surfactant, water, and NaCl has an optimal salinity that does not depend on overall surfactant concentration. SPEJ P. 971^

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