Mechanistic Modeling of Alkaline/Surfactant/Polymer Floods

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.

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 ◽  
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.


2020 ◽  
Vol 10 (11) ◽  
pp. 3752 ◽  
Author(s):  
Shabrina Sri Riswati ◽  
Wisup Bae ◽  
Changhyup Park ◽  
Asep K. Permadi ◽  
Adi Novriansyah

This paper presents a nonionic surfactant in the anionic surfactant pair (ternary mixture) that influences the hydrophobicity of the alkaline–surfactant–polymer (ASP) slug within low-salinity formation water, an environment that constrains optimal designs of the salinity gradient and phase types. The hydrophobicity effectively reduced the optimum salinity, but achieving as much by mixing various surfactants has been challenging. We conducted a phase behavior test and a coreflooding test, and the results prove the effectiveness of the nonionic surfactant in enlarging the chemical applicability by making ASP flooding more hydrophobic. The proposed ASP mixture consisted of 0.2 wt% sodium carbonate, 0.25 wt% anionic surfactant pair, and 0.2 wt% nonionic surfactant, and 0.15 wt% hydrolyzed polyacrylamide. The nonionic surfactant decreased the optimum salinity to 1.1 wt% NaCl compared to the 1.7 wt% NaCl of the reference case with heavy alcohol present instead of the nonionic surfactant. The coreflooding test confirmed the field applicability of the nonionic surfactant by recovering more oil, with the proposed scheme producing up to 74% of residual oil after extensive waterflooding compared to 51% of cumulative oil recovery with the reference case. The nonionic surfactant led to a Winsor type III microemulsion with a 0.85 pore volume while the reference case had a 0.50 pore volume. The nonionic surfactant made ASP flooding more hydrophobic, maintained a separate phase of the surfactant between the oil and aqueous phases to achieve ultra-low interfacial tension, and recovered the oil effectively.


SPE Journal ◽  
2015 ◽  
Vol 21 (01) ◽  
pp. 10-21 ◽  
Author(s):  
Jeffrey G. Southwick ◽  
Esther van den Pol ◽  
Carl H. van Rijn ◽  
Diederik W. van Batenburg ◽  
Diederik Boersma ◽  
...  

Summary Ammonia is logistically preferred over sodium carbonate for alkaline/surfactant/polymer (ASP) enhanced-oil-recovery projects because of its low molar mass and the possibility for it to be delivered as a liquid. On an offshore platform, space and weight savings can be the determining factor in deciding whether an ASP project is feasible. Logistics may also be critical in determining the economic feasibility of projects in remote locations. Ammonia as alkali together with a surfactant blend of alkyl propoxy sulfate/internal olefin sulfonate (APS/IOS) functions as an effective alkali. Surfactant adsorption is low, and oil recovery in corefloods is high. Static adsorption tests show that low surfactant adsorption is attained at pH >9, a condition that ammonia satisfies at low solution concentration. It is expected that ammonia has a performance deficiency relative to sodium carbonate in that it does not precipitate calcium from solution. Calcium accumulation in the ammonia ASP solution will occur, caused by ion exchange from clays. The high oil recovery for ammonia and the calcium accumulation in ASP and surfactant/polymer corefloods with APS/IOS blends show that this surfactant system is effective and calcium-tolerant. Also, phase behavior and interfacial-tension (IFT) measurements suggest that APS/IOS blends remain effective in the presence of calcium. Ethylene oxide/propylene oxide sulfates (such as the used APS) are known commercially available, calcium-tolerant surfactants. However, because of hydrolysis, sulfate-type surfactants are suitable for use only in lower-temperature reservoirs. Very different behavior was noticed for phase-behavior measurements with calcium-intolerant surfactants such as alkyl benzene sulfonates and IOS. In this case, calcium addition results in a very high IFT and complete separation of oil and brine. Presumably, this will result in low oil recovery. A preferred approach for ASP offshore with divalent-ion-intolerant surfactants may be the use of a hybrid alkali system combining the attributes of sodium carbonate and ammonia. The concept is to supply the bulk of the alkalinity for an ASP flood by ammonia with all the inherent logistical advantages. A minor quantity of sodium carbonate is added to the formulation to specifically precipitate calcium ions.


SPE Journal ◽  
2016 ◽  
Vol 21 (01) ◽  
pp. 32-54 ◽  
Author(s):  
Aboulghasem Kazemi Korrani ◽  
Kamy Sepehrnoori ◽  
Mojdeh Delshad

Summary Mechanistic simulation of alkaline/surfactant/polymer (ASP) flooding considers chemical reactions between the alkali and the oil to form in-situ soap and reactions between the alkali and the minerals and brine. A comprehensive mechanistic modeling of such process remains a challenge, mainly caused by the complicated ASP phase behavior and the complexity of geochemical reactions that occur in the reservoir. Because of the lack of the microemulsion phase and/or lack of reactions that may lead to the consumption of alkali and resulting lag in the pH, a simplified ASP phase behavior is often used. A state-of-the-art geochemical package, IPhreeqc, of the United States Geological Survey was coupled with UTCHEM, an in-house research chemical-flooding reservoir simulator developed at The University of Texas at Austin (UT), for a robust, flexible, and accurate integrated tool to mechanistically model ASP floods. UTCHEM has a comprehensive three-phase (water, oil, microemulsion) flash package for the mixture of surfactant and soap as a function of salinity, temperature, and cosolvent concentration. Through this integrated tool, we are able to simulate homogeneous and heterogeneous (mineral dissolution/precipitation), irreversible, surface complexation, and ion exchange reactions under nonisothermal, nonisobaric, and both local-equilibrium and kinetic conditions. Italic words are defined in Appendix A. IPhreeqc has rich databases of chemical species and also the flexibility to include the alkaline reactions required for modeling ASP floods. Hence, to the best of our knowledge, for the first time, the important aspects of ASP flooding are considered. An algorithm is presented for modeling the geochemistry in an implicit-in-pressure-and-explicit-in-concentration solution algorithm. Finally, we show how to apply the integrated tool, UTCHEM-IPhreeqc, to match three different reaction-related chemical-flooding processes: ASP flooding in an acidic active crude oil, ASP flooding in a nonacidic crude oil, and alkaline/cosolvent/polymer flooding.


2015 ◽  
Vol 137 (1) ◽  
Author(s):  
Mahmood Reza Yassin ◽  
Shahab Ayatollahi ◽  
Behzad Rostami ◽  
Kamran Hassani ◽  
Vahid Taghikhani

Based on the conventional approach, the trapped oil in rock pores can be easily displaced when a Winsor type (III) micro-emulsion is formed in the reservoir during surfactant flooding. On the other hand, the Winsor type (III) involves three phase flow of water, oil, and micro-emulsion that causes considerable oil phase trapping and surfactant retention. This work presents an experimental study on the effect of micro-emulsion phase behavior during surfactant flooding in sandstone and carbonate core samples. In this study, after accomplishing salinity scan of a cationic surfactant (C16–N(CH3)3Br), the effects of Winsor (I), Winsor (III) and Winsor (II) on oil recovery factor, differential pressure drop, relative permeability, and relative permeability ratio were investigated extensively. To carry out a comparative study, homogeneous and similar sandstone and carbonate rocks were selected and the effects of wettability alteration and dynamic surfactant adsorption were studied on them. The results of oil recovery factor in both rock types showed that Winsor (I) and Winsor (III) are preferred compared to Winsor (II) phase behavior. In addition, comparison of normalized relative permeability ratio at high water saturations revealed that Winsor (I) has more appropriate oil and water relative permeability than Winsor (II). The results presented in this paper demonstrate that optimum salinity which results in higher recovery factor and better oil displacement may occur at salinities out of Winsor (III) range. Therefore, the best way to specify optimum salinity is to perform core flood experiments at several salinities, which cover all phase behaviors of Winsor (I), Winsor (III), and Winsor (II).


2021 ◽  
Vol 3 (5) ◽  
Author(s):  
Ruissein Mahon ◽  
Gbenga Oluyemi ◽  
Babs Oyeneyin ◽  
Yakubu Balogun

Abstract Polymer flooding is a mature chemical enhanced oil recovery method employed in oilfields at pilot testing and field scales. Although results from these applications empirically demonstrate the higher displacement efficiency of polymer flooding over waterflooding operations, the fact remains that not all the oil will be recovered. Thus, continued research attention is needed to further understand the displacement flow mechanism of the immiscible process and the rock–fluid interaction propagated by the multiphase flow during polymer flooding operations. In this study, displacement sequence experiments were conducted to investigate the viscosifying effect of polymer solutions on oil recovery in sandpack systems. The history matching technique was employed to estimate relative permeability, fractional flow and saturation profile through the implementation of a Corey-type function. Experimental results showed that in the case of the motor oil being the displaced fluid, the XG 2500 ppm polymer achieved a 47.0% increase in oil recovery compared with the waterflood case, while the XG 1000 ppm polymer achieved a 38.6% increase in oil recovery compared with the waterflood case. Testing with the motor oil being the displaced fluid, the viscosity ratio was 136 for the waterflood case, 18 for the polymer flood case with XG 1000 ppm polymer and 9 for the polymer flood case with XG 2500 ppm polymer. Findings also revealed that for the waterflood cases, the porous media exhibited oil-wet characteristics, while the polymer flood cases demonstrated water-wet characteristics. This paper provides theoretical support for the application of polymer to improve oil recovery by providing insights into the mechanism behind oil displacement. Graphic abstract Highlights The difference in shape of relative permeability curves are indicative of the effect of mobility control of each polymer concentration. The water-oil systems exhibited oil-wet characteristics, while the polymer-oil systems demonstrated water-wet characteristics. A large contrast in displacing and displaced fluid viscosities led to viscous fingering and early water breakthrough.


2021 ◽  
pp. 1-18
Author(s):  
Gisela Vanegas ◽  
John Nejedlik ◽  
Pascale Neff ◽  
Torsten Clemens

Summary Forecasting production from hydrocarbon fields is challenging because of the large number of uncertain model parameters and the multitude of observed data that are measured. The large number of model parameters leads to uncertainty in the production forecast from hydrocarbon fields. Changing operating conditions [e.g., implementation of improved oil recovery or enhanced oil recovery (EOR)] results in model parameters becoming sensitive in the forecast that were not sensitive during the production history. Hence, simulation approaches need to be able to address uncertainty in model parameters as well as conditioning numerical models to a multitude of different observed data. Sampling from distributions of various geological and dynamic parameters allows for the generation of an ensemble of numerical models that could be falsified using principal-component analysis (PCA) for different observed data. If the numerical models are not falsified, machine-learning (ML) approaches can be used to generate a large set of parameter combinations that can be conditioned to the different observed data. The data conditioning is followed by a final step ensuring that parameter interactions are covered. The methodology was applied to a sandstone oil reservoir with more than 70 years of production history containing dozens of wells. The resulting ensemble of numerical models is conditioned to all observed data. Furthermore, the resulting posterior-model parameter distributions are only modified from the prior-model parameter distributions if the observed data are informative for the model parameters. Hence, changes in operating conditions can be forecast under uncertainty, which is essential if nonsensitive parameters in the history are sensitive in the forecast.


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