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

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.

2009 ◽  
Vol 12 (04) ◽  
pp. 518-527 ◽  
Author(s):  
Hourshad Mohammadi ◽  
Mojdeh Delshad ◽  
Gary A. Pope

Summary Alkaline/surfactant/polymer (ASP) flooding is of increasing interest and importance because of high oil prices and the need to increase oil production. The benefits of combining alkali with surfactant are well established. The alkali has very important benefits such as lowering interfacial tension (IFT) and reducing adsorption of anionic surfactants that decrease costs and make ASP a very attractive enhanced-oil-recovery method, provided that the consumption is not too large and the alkali can be propagated at the same rate as the synthetic surfactant and polymer. However, the process is complex, so it is important that new candidates for ASP be selected taking into account the numerous chemical reactions that occur in the reservoir. The reaction of acid and alkali to generate soap and its subsequent effect on phase behavior is the most crucial for crude oils containing naphthenic acids. Mechanistic simulation of the ASP flood considering the chemical reactions, alkali consumption, and soap generation and the effect on the phase behavior is the key to success of future field operations. Using numerical models, the process can be designed and optimized to ensure the proper propagation of alkali and effective soap and surfactant concentrations to promote low IFT and a favorable salinity gradient. In this paper, we describe the ASP module of the UTCHEM simulator, which is the University of Texas chemical compositional simulator, with particular attention to phase behavior and the effect of soap on optimum salinity and solubilization ratio. Phase behavior data are presented for sodium carbonate and a blend of surfactants with an acidic crude oil that followed the conventional Winsor phase transition with significant three-phase regions even at low surfactant concentrations. The solubilization data at different oil concentrations were successfully modeled using Hand's rule. Optimum salinity and solubilization ratio were correlated with soap mole fractions using mixing rules. ASP coreflood results were successfully modeled taking into account the aqueous reactions, alkali/rock interactions, and phase behavior of soap and surfactant. Mechanistic simulations give insights into the propagation of alkali, soap, and surfactant in the core and aid in future coreflood and field-scale ASP designs.


2021 ◽  
Author(s):  
Nancy Chun Zhou ◽  
Meng Lu ◽  
Fuchen Liu ◽  
Wenhong Li ◽  
Jianshen Li ◽  
...  

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.


SPE Journal ◽  
2018 ◽  
Vol 24 (02) ◽  
pp. 647-659 ◽  
Author(s):  
V. A. Torrealba ◽  
R. T. Johns ◽  
H.. Hoteit

Summary An accurate description of the microemulsion-phase behavior is critical for many industrial applications, including surfactant flooding in enhanced oil recovery (EOR). Recent phase-behavior models have assumed constant-shaped micelles, typically spherical, using net-average curvature (NAC), which is not consistent with scattering and microscopy experiments that suggest changes in shapes of the continuous and discontinuous domains. On the basis of the strong evidence of varying micellar shape, principal micellar curves were used recently to model interfacial tensions (IFTs). Huh's scaling equation (Huh 1979) also was coupled to this IFT model to generate phase-behavior estimates, but without accounting for the micellar shape. In this paper, we present a novel microemulsion-phase-behavior equation of state (EoS) that accounts for changing micellar curvatures under the assumption of a general-prolate spheroidal geometry, instead of through Huh's equation. This new EoS improves phase-behavior-modeling capabilities and eliminates the use of NAC in favor of a more-physical definition of characteristic length. Our new EoS can be used to fit and predict microemulsion-phase behavior irrespective of IFT-data availability. For the cases considered, the new EoS agrees well with experimental data for scans in both salinity and composition. The model also predicts phase-behavior data for a wide range of temperature and pressure, and it is validated against dynamic scattering experiments to show the physical significance of the approach.


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).


SPE Journal ◽  
2007 ◽  
Vol 12 (03) ◽  
pp. 322-338 ◽  
Author(s):  
Choongyong Han ◽  
Mojdeh Delshad ◽  
Kamy Sepehrnoori ◽  
Gary Arnold Pope

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.


2021 ◽  
Author(s):  
Adekunle Tirimisiyu Adeniyi ◽  
Ijoma Onyemaechi

Abstract After the primary and secondary oil recoveries, a substantial amount of oil is left in the reservoir which can be recovered by tertiary methods like the Alkaline-Surfactant Flood. Reasons for having some unproduced hydrocarbon in the reservoir include and not limited to the following; forces of attraction fluid contacts, low permeability, high viscous fluid, poor swept efficiency, etc. Although, it is possible to commence waterflooding together chemical injection at the start of production. Reservoir simulation with commercial simulator, could guide in selecting the most appropriate period to commence chemical flooding. In this study, the performance of a new synthetic surfactant produced from Jatropha Curcas seed was compared with that of a selected commercial surfactant in the presence of an alkaline and this shows that the non-edible Jatropha oil is a natural, inexpensive and a renewable source of energy for the production of anionic surfactants and a good substitute for commercial surfactants like Sodium Dodecyl Sulphate (SDS). The Methyl Ester Sulfonate (MES) surfactant showed no precipitation or cloudiness during stability test and was able to reduce the Interfacial Tension (IFT) to 0.018 mN/m and 0.020 mN/m in the presence of sodium carbonate and sodium hydroxide respectively as alkaline at low surfactant concentration. The optimum alkaline surfactant formulation in terms of oil recovery performance obtained from the core flooding experiment corresponds to a concentration of sodium carbonate (0.5wt%), sodium hydroxide (0.5wt%) mixed in distilled water and Methyl Ester Sulfonate (MES) surfactant (1wt%). The injection of 0.5 percentage volume of alkaline surfactant slug produced an incremental oil recovery of 26.7% and 29% respectively. With these incremental oil recoveries, increasing demand for hydrocarbons product could be met, and returns on investment portfolio will be improved.


SPE Journal ◽  
2013 ◽  
Vol 18 (03) ◽  
pp. 428-439 ◽  
Author(s):  
M.. Roshanfekr ◽  
R.T.. T. Johns ◽  
M.. Delshad ◽  
G.A.. A. Pope

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.


Langmuir ◽  
2016 ◽  
Vol 32 (35) ◽  
pp. 8969-8979 ◽  
Author(s):  
Soumyadeep Ghosh ◽  
Russell T. Johns

1978 ◽  
Vol 18 (05) ◽  
pp. 339-354 ◽  
Author(s):  
G.A. Pope ◽  
R.C. Nelson

Abstract A one-dimensional, compositional, chemical-flood simulator was developed to calculate oil recovery as a function of several major process variables. The principal relationships included are phase behavior and interfacial tensions as a function of electrolyte and surfactant concentrations, and polymer viscosity as a function of electrolyte and polymer viscosity as a function of electrolyte and polymer concentration. Emphasis was on studying the polymer concentration. Emphasis was on studying the process itself, especially complex interactions that process itself, especially complex interactions that occur because of two- and three-phase behavior, interfacial tension, fractional flow, dispersion, adsorption, cation exchange, chemical slug size, and polymer transport. Introduction Nelson and Pope reported laboratory flow results in which phase behavior plays a key role in oil recovery by chemical flooding. They show that many characteristics of chemical floods can be explained by considering the equilibrium mixing and transport of surfactant/brine/oil systems in light of phase behavior observed in external mixtures. phase behavior observed in external mixtures. Although based on highly idealized representations of the key properties involved, we believe that the simulator described here can yield significant insight into phase-related process mechanisms, such as "oil swelling," the interactions among process variables, and the relative merit of various process variables, and the relative merit of various chemical flooding strategies. The framework for systematically improving the compositional aspects of numerical simulation of chemical flooding is evident with our approach. This is because a completely compositional model based on total concentrations, rather than saturations, is assumed from the start. Then, the calculation of phase concentrations, and from them phase saturations, for any desired number of phase saturations, for any desired number of components and phases with any type phase behavior is a relatively simple matter. Conceptually, mathematically, and numerically, this approach is simpler and easier to use than the traditional approach used in reservoir engineering simulation, although in principle they can be made equivalent. The cases illustrated here are for up to six components and up to three phases, using highly simplified representations of the binodal and distribution curves for the surfactant/brine/oil systems and the properties of the various phases that form. Even so, as many as 64 parameters are required to specify the process. ASSUMPTIONS, EQUATIONS, AND NUMERICAL TECHNIQUE The basic assumptions of the model are as follow.The system is one-dimensional and homogeneous in permeability and porosity.Local thermodynamic equilibrium exists everywhere.The total mixture volume does not change when mixing individual components (delta VM = 0).Gravity and capillary pressure are negligible.Fluid properties are a function of composition only.Darcy's law applies.Physical dispersion can be approximated adequately with numerical dispersion by selecting the appropriate grid size and time step. Additional assumptions are required to model various properties such as interfacial tension, viscosity, etc. However, for the most part, these are changed readily by the user and are not considered as basic as the above assumptions, which also can be relaxed, but only with considerably more effort. The auxiliary assumptions will be given, therefore, with the specific examples discussed below. Given the above assumptions, the continuity equations for each component i and np phases are (1) SPEJ P. 339


1981 ◽  
Vol 21 (05) ◽  
pp. 573-580 ◽  
Author(s):  
J.H. Bae ◽  
C.B. Petrick

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^


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