Observations on the Coalescence Behavior of Oil Droplets and Emulsion Stability in Enhanced Oil Recovery

1978 ◽  
Vol 18 (06) ◽  
pp. 409-417 ◽  
Author(s):  
D.T. Wasan ◽  
S.M. Shah ◽  
N. Aderangi ◽  
M.S. Chan ◽  
J.J. McNamara

Original manuscript received in Society of Petroleum Engineers office Sept. 20, 1977. Paper accepted for publication June 2, 1978. Revised manuscript received Aug. 2, 1978. Paper (SPE 6846) was presented at SPE-AIME 52nd Annual Fall Technical Conference and Exhibition, held in Denver, Oct. 9-12, 1977. Abstract Results of experiments on the coalescence of crude oil drops at an oil-water interface and interdroplet coalescence in crude oil-water emulsions containing petroleum sulfonates and cosurfactant as surfactant systems with other chemical additives were analyzed in terms of interracial viscosity, interfacial tension, interfacial charge, and thickness of the films surrounding the microdroplets. A qualitative correlation was found between coalescence rates and interfacial viscosities; however, there appears to be no direct correlation with interfacial tension. New insight has been gained into the influence of emulsion stability in tertiary oil recovery by surfactant/polymer flooding in laboratory core tests. We concluded that those systems that result in relatively stable emulsions yield poor coalescence rates and, hence, poor oil recovery, Introduction The ability of the surfactant/polymer system to initiate and to propagate an oil bank is the single most important feature of a successful tertiary oil-recovery process. The mechanisms of oil-bank formation and development are yet unknown. It has been suggested that without the initiation of the oil bank, the process behaves more like the unstable injection of a surfactant solution alone, where the oil is produced by entrainment or emulsification in the flowing surfactant stream. In a laboratory study of the initial displacement of residual hydrocarbons by aqueous surfactant solutions, Childress and Schechter and Wade observed that those systems that spontaneously emulsified and coalesced rapidly yielded better oil recovery than those systems that spontaneously formed stable emulsions. Recently, Strange and Talash, Whitley and Ware, and Widmeyer et al. reported results of Salem (IL) low-tension, water-flood tests that used Witco TRS 10-80 TM petroleum sulfonate surfactant solution. They found stable oil-in-water emulsions at the observer well in addition to emulsion problems at the production well and reported that problems at the production well and reported that actual oil recovery was about one-quarter the target value. These studies clearly suggested that poor efficiency of oil recovery results from emulsion stability problems in the low-tension surfactant or micellar processes. Vinatieri presented results of experiments on the stability of crude-oil-in-water emulsions that coo be produced during a surfactant or micellar flood. More recently, we have assessed the rigidity of interfacial films and its relationship to coalescence rate through measurements of interfacial viscosities of crude oils contacted against aqueous solutions containing various concentrations of surfactants and other pertinent chemical additives. Our data clearly indicate that in the absence of a commercial surfactant, interfacial viscosity builds up rapidly, coalescence is inhibited, and the resulting emulsion is quite stable. These phenomena also have been observed by Gladden and Neustadter. Several studies were conducted on the structure of film-forming material at the crude oil/water interface, its effect on emulsion stability, and the role of such films in oil recovery by water or caustic solution displacements. Rigid films were found to reduce the amount of oil recovered. Our studies also have shown that the addition of a commercial surfactant lowered both the interfacial viscosity (ISV) and interfacial tension (IFT) of the crude oil-aqueous solution system. However, the concentration at which both the IFT and ISV are minimized cannot be identified by measuring IFT alone. We have conducted a cinephotomicrographic examination of spontaneous emulsification and a microvisual study of the displacement of residual crude oil by aqueous surfactant solutions in micromodel porous media. SPEJ P. 409

1982 ◽  
Vol 22 (04) ◽  
pp. 472-480 ◽  
Author(s):  
S.L. Enedy ◽  
S.M. Farouq Ali ◽  
C.D. Stahl

Abstract This investigation focused on developing an efficient chemical flooding process by use of dilute surfactant/polymer slugs. The competing roles of interfacial tension (IFT) and equivalent weight (EW) of the surfactant used, as well as the effect of different types of preflushes on tertiary oil recovery, were studied. Volume of residual oil recovered per gram of surfactant used was examined as a function of these variables and slug size. Tertiary oil recovery increased with an increase in the dilute surfactant slug size and buffer viscosity. However, low IFT does not ensure high oil recovery. An increase in surfactant EW used actually can lead to a decrease in oil recovery. Tertiary oil recovery was also sensitive to preflush type. Reasons for the observed behavior are examined in relation to the surfactant properties as well as to adsorption and retention. Introduction Two approaches are being used in development of surfactant /polymer-type chemical floods:a small-PV slug of high surfactant concentration, ora large-PV slug of low surfactant concentration. This study deals with the latter-i.e., dilute aqueous slugs (with polymer added in many cases) containing less than or equal 2.0 wt% sulfonates and about 0. 1 wt% crude oil. Because the dilute slug contains little of the dispersed phase, an aqueous surfactant slug usually is unable to displace the oil miscibly; however, residual brine is miscible with the slug if the inorganic salt concentration is not excessive. The dilute, aqueous petroleum sulfonate slug lowers the oil/water IFT. overcoming capillary forces. This process commonly is referred to as locally immiscible oil displacement. Objectives The objective of this work was to develop an efficient dilute surfactant/polymer slug for the Bradford crude with a variety of sulfonate combinations. Effects of varying the slug characteristics such as equivalent weight, IFT, salt concentration, etc. on tertiary oil recovery were examined. Materials and Experimental Details The petroleum sulfonates and the dilute slugs used in this study are listed in Tables 1 and 2, respectively. The crude oil tested was Bradford crude 144 degrees API (0.003 g/cm3), 4 cp (0.004 Pa.s)]. The polymer solutions were prefiltered and driven by brines of various concentrations (0.02, 1.0, and 2.0% NACl). In many cases, the polymer was added to the slug. Conventional coreflood equipment described in Ref. 3 was used. Berea sandstone cores (unfired) 2 in, (5 cm) in diameter and 4 ft (1.3 m) in length were used for all tests, with a new core for each test. Porosity ranged from 19.3 to 21.0%, permeability averaged 203 md, and the waterflood residual oil saturation averaged 33.1%. IFT's were measured by the spinning drop method. Viscosities were measured with a Brookfield viscosimeter and are reported here for 6 rpm (0.1 rev/s). The dilute slugs containing polymer exhibited non-Newtonian behavior. Without polymer the behavior was Newtonian. Sulfonate concentration in the oleic phase was determined by an infrared spectrophotometer, while the concentration in the aqueous phase was measured by ultraviolet (UV) absorbance analysis. Discussion of Results Slug development in this investigation was an evolutionary process. Dilute slugs were developed and core tested in a sequential manner (Table 2). Slugs 100 through 200 yielded insignificant ternary oil recoveries (largely because of excessive adsorption and retention), but the results helped determine improvements in slug compositions and in the overall chemical flood. This paper gives results for the more efficient slugs only. SPEJ P. 472^


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^


2021 ◽  
Vol 5 (3) ◽  
pp. 42
Author(s):  
Ronald Marquez ◽  
Johnny Bullon ◽  
Ana Forgiarini ◽  
Jean-Louis Salager

The oscillatory spinning drop method has been proven recently to be an accurate technique to measure dilational interfacial rheological properties. It is the only available equipment for measuring dilational moduli in low interfacial tension systems, as it is the case in applications dealing with surfactant-oil-water three-phase behavior like enhanced oil recovery, crude oil dehydration, or extreme microemulsion solubilization. Different systems can be studied, bubble-in-liquid, oil-in-water, microemulsion-in-water, oil-in-microemulsion, and systems with the presence of complex natural surfactants like asphaltene aggregates or particles. The technique allows studying the characteristics and properties of water/oil interfaces, particularly when the oil contains asphaltenes and when surfactants are present. In this work, we present a review of the measurements of crude oil-brine interfaces with the oscillating spinning drop technique. The review is divided into four sections. First, an introduction on the oscillating spinning drop technique, fundamental and applied concepts are presented. The three sections that follow are divided according to the complexity of the systems measured with the oscillating spinning drop, starting with simple surfactant-oil-water systems. Then the complexity increases, presenting interfacial rheology properties of crude oil-brine systems, and finally, more complex surfactant-crude oil-brine systems are reviewed. We have found that using the oscillating spinning drop method to measure interfacial rheology properties can help make precise measurements in a reasonable amount of time. This is of significance when systems with long equilibration times, e.g., asphaltene or high molecular weight surfactant-containing systems are measured, or with systems formulated with a demulsifier which is generally associated with low interfacial tension.


Fuel ◽  
2017 ◽  
Vol 191 ◽  
pp. 239-250 ◽  
Author(s):  
Sivabalan Sakthivel ◽  
Sugirtha Velusamy ◽  
Vishnu Chandrasekharan Nair ◽  
Tushar Sharma ◽  
Jitendra S. Sangwai

2018 ◽  
Vol 11 (1) ◽  
pp. 118-128
Author(s):  
Hongbo Fang ◽  
Mingxia Wang ◽  
Xiaoyun Liu ◽  
Weinan Jin ◽  
Xiangyang Ma ◽  
...  

Background: A hydraulic fracture is a key technology to increase production of the low permeability oil fields. Fracture additives such as gels, friction reducers, pH adjusters and clay stabilizers were injected into the underground. While more than 50% of the fracture fluid remains underground. The residue of fracture fluid comes out with the produced liquid (a mixture of crude oil and water) in the subsequent oil recovery process, which results in a highly stable crude oil-water emulsion. Objective: The stability and stable mechanism of the emulsion with fracture fluid have been experimentally investigated. Materials and Methods: The influences of fracture additives and components of crude oil on the stability of emulsion were investigated by bottle test and microscopic examination. The interfacial tension and modulus of dilation were explored by a spinning drop interfacial tension meter and an interface expansion rheometer, respectively. Results: The fracture additives played the key role on the emulsion stability. On one hand, the interface energy of oil-water was reduced by friction reducer (IFT was decreased from 24.0 mN/m to 1.9 mN/m), which was a favor for the formation of an emulsion. On the other hand, the dilational modulus of crude oil-water film was increased by hydroxypropyl guar and pH adjuster (Na2CO3) to form a viscoelastic film, which resulted in a highly stable emulsion. Conclusion: The residual fracture fluid accompanied by produced liquid resulted in a highly stable emulsion. The emulsion with fracture additives was difficult to be broken, which may affect the normal production of the oil field. A positive strategy such as developing demulsifier with high efficient should be put onto the schedule.


Energies ◽  
2021 ◽  
Vol 14 (19) ◽  
pp. 6234
Author(s):  
Xu Jiang ◽  
Ming Liu ◽  
Xingxun Li ◽  
Li Wang ◽  
Shuang Liang ◽  
...  

Surfactants and nanoparticles play crucial roles in controlling the oil-water interfacial phenomenon. The natural oil-wet mineral nanoparticles that exist in crude oil could remarkably affect water-oil interfacial characteristics. Most of recent studies focus on the effect of hydrophilic nanoparticles dispersed in water on the oil-water interfacial phenomenon for the nanoparticle enhanced oil recovery. However, studies of the impact of the oil-wet nanoparticles existed in crude oil on interfacial behaviour are rare. In this study, the impacts of Span 80 surfactant and hydrophobic SiO2 nanoparticles on the crude oil-water interfacial characteristics were studied by measuring the dynamic and equilibrium crude oil-water interfacial tensions. The results show the existence of nanoparticles leading to higher crude oil-water interfacial tensions than those without nanoparticles at low surfactant concentrations below 2000 ppm. At a Span 80 surfactant concentration of 1000 ppm, the increase of interfacial tension caused by nanoparticles is largest, which is around 8.6 mN/m. For high Span 80 surfactant concentrations, the less significant impact of nanoparticles on the crude oil-water interfacial tension is obtained. The effect of nanoparticle concentration on the crude oil-water interfacial tension was also investigated in the existence of surfactant. The data indicates the less significant influence of nanoparticles on the crude oil-water interfacial tension at high nanoparticle concentration in the presence of Span 80 surfactant. This study confirms the influences of nanoparticle-surfactant interaction and competitive surfactant molecule adsorption on the nanoparticles surfaces and the crude oil-water interface.


2019 ◽  
Vol 818 ◽  
pp. 62-71
Author(s):  
Harvin Kaur ◽  
Azuraien Jaafar

In the industry, stubborn emulsion still constitutes up to 20% of the total emulsion volume. The existing remediation strategies for emulsion treatment rely heavily on the study of heavy crude oil emulsion. However, minimal information is available on integrating interfacial rheology with emulsion stability on waxy crude oil emulsion. The proposed research provides a study to the development of integration between interfacial rheology and emulsion stability so that it can be a quick assessment but an accurate method to measure emulsion stability. The primary objectives of the research are to provide an extensional study to the design development of a comprehensive interfacial rheology protocol for the assessment of emulsion stability by developing a method of testing and monitoring the interfacial rheology and to investigate the demulsification ability of the waxy crude oil emulsion subjected to microbial treatment. The novelty of this study is to use the newly developed measurement protocol via interfacial rheology to predict emulsion stability. Application of the microbes on waxy crude oil to breakdown the water-in-oil emulsion using a rheometer will also be explored. The treatment is targeted to disintegrate the interfacial layer within the emulsion leading to better oil recovery. Rheological properties of the emulsion will be monitored upon the microbial injection to analyze the effects of the treatment on the rheology of emulsion. The outcomes from this research is that the newly developed protocol will predict emulsion stability that could resolve the stubborn emulsion issues via the developed interfacial rheology protocol, which could be time-saving and increases the production efficiency. This research paper is a study to develop a correlation on surface tension and interfacial tension between crude oil, water and a readily-mixed emulsion.


1981 ◽  
Vol 21 (04) ◽  
pp. 493-499 ◽  
Author(s):  
J.H. Runnels ◽  
C.J. Engel

Abstract An procedure is given for separating surfactant precursors that occur in some crude oils. The effect of the precursors on the properties of the oils are described also. The separations were made by silica gel chromatography on crude oil from which the asphaltenes had been removed. The effect of the precursors on the properties of the crude was evaluated by blending the surfactant precursors into the original oil, a modified oil, or a hydrocarbon solvent such as benzene. Precursors activated and converted to surface active materials by a strong base such as sodium hydroxide are effective in reducing the interfacial tension between the oil and aqueous phase. Occurrence of precursors in crude oils is essential for improved oil recovery by the causticflood process. The procedure for separating the precursors should provide a viable means for evaluating the applicability of a causticflood tertiary oil recovery process to a particular crude or reservoir. Introduction Tertiary oil recovery by the causticflood process is inherently dependent on naturally occurring surfactant precursors in the crude. The surfactant precursors react with the caustic (base) in the floodwater to form surface active compounds that reduce the interfacial tension between the crude and aqueous phase, alter the wettability of the mineral surfaces, or reduce rigid film formation at the crude/aqueous interface. In laboratory oil-recovery tests, these mechanisms stimulate oil production characterized by increased production at caustic breakthrough and a high oil/water ratio after breakthrough. An early effort to identify the surfactant precursors in a Rio Bravo (CA) crude concluded that the surfactant precursors were related closely to the asphaltene and resin fractions of the crude. Subsequent studies using an Eichlingen Niedersachen (West German) crude and a Ventura (CA) crude concluded that the surfactant precursors were acids and phenols, respectively. The extensive work of Seifert established that the surfactant precursors of a Ventura crude were carboxylic acids and that the phenolic components of the crude were interfacially inactive. The purpose of our study was to develop a simple and practical method of separating surfactant precursors from crude oil and to evaluate their effect on the interfacial tension, acid number, and other properties of the crude. The separation technique was developed using Smackover Nacatoch crude and the surfactant precursors evaluated were obtained from the same crude. Description of Smackover Nacatoch Crude The Smackover reservoir is located in southern Arkansas, and the Nacatoch pay zone is the shallowest of five pay zones. The crude has an API gravity of 21 degrees, a viscosity of 160 cp at room temperature, and is produced from an unconsolidated sand formation about 2,000 ft deep. Preliminary studies showed that the interfacial tension between the crude and an aqueous phase was reduced from about 12 to 0.02 dyne/cm when the pH of the aqueous phase was increased from 7.0 to 12.5 with sodium hydroxide. The significant reduction in interfacial tension at higher pH's indicated that the crude contained a relatively high concentration of surfactant precursors that were converted to surface active materials by sodium hydroxide. SPEJ P. 493^


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