Adsorption of Anionic Surfactants in Sandstones: Impact of Sacrificial Agents

2021 ◽  
Author(s):  
Gulcan Bahar Koparal ◽  
Himanshu Sharma ◽  
Pathma J. Liyanage ◽  
Krishna K. Panthi ◽  
Kishore Mohanty

Abstract High surfactant adsorption remains a bottleneck for a field-wide implementation of surfactant floods. Although alkali addition lowers surfactant adsorption, alkali also introduces many complexities. In our systematic study, we investigated a simple and cost effective method to lower surfactant adsorption in sandstones without adding unnecessary complexities. Static and dynamic surfactant adsorption studies were conducted to understand the role of sacrificial agent sodium polyacrylate (NaPA) on adsorption of anionic surfactants n outcrop and resevoir sandstone corefloods. The dynamic retention studies were conducted with and without the presence of crude oil. Surfactant phase behavior studies were first conducted to identify surfactant blends that showed ultralow interfacial tension (IFT) with two crude oils at reservoir temperature (40°C). Base case dynamic retention data, in the absence of crude oil, was obtained for these surfactant formulations at their respective optimum salinities. NaPA was then added to these surfactant formulations and similar adsorption tests were conducted. Finally, oil recovery SP corefloods were conducted for each surfactant formulations, with and without adding NaPA, and oil recovery data including the surfactant retention was compared. Static adsorption of these surfactant formulations at their respective optimum salinities on crushed sandstone varied from 0.42-0.74 mg/g-rock. Their respective adsorptions lowered to 0.37-0.49 mg/g-rock on adding a small amount of NaPA. Surfactant retention in single-phase dynamic SP corefloods in the absence of crude oil in outcrop Berea cores was between 0.17 to 0.23 mg/g-rock. On adding a small amount of NaPA, the surfactant adsorption values lowered to 0.1 mg/g-rock. Oil recovery SP corefloods showed high oil recovery (~91% ROIP) and low surfactant retention (~0.1 mg/g-rock) on adding NaPA to the surfactant formulations.

1981 ◽  
Vol 21 (04) ◽  
pp. 500-512 ◽  
Author(s):  
K.O. Meyers ◽  
S.J. Salter

Abstract Static adsorption measurements of petroleum sulfonates on crushed Bell Creek and Berea cores were made using fluids with the same active surfactant concentration but varying brine/oil mass ratios. The salinity of the brine was chosen such that a significant three-phase region existed in the oil/brine/surfactant/alcohol system. The surfactant adsorption was found to be independent of the structural and compositions differences among the fluids. A series of oil recovery tests in which middle-phase microemulsions were injected into waterflooded cores also were performed. The cores used in these tests had been treated to remove divalent ions accessible to fluid flow. Microemulsion slugs (1.75 to 146% PV) of equal active surfactant concentration but differing brine/oil mass ratios were injected. The total surfactant retention for this system was also found to be independent of the brine/oil mass ratio. Introduction Control of sulfonate loss is one of the single most important factors in determining the success or failure of a surfactant flooding process. In a typical surfactant flood, sulfonate costs are frequently half or more of the total project cost. As a result, this area has been studied frequently. Many authors have studied detailed adsorption mechanisms - mostly from aqueous solutions and at relatively low concentrations. A recent thesis from the U. of Texas1 and its references provide an excellent description of this type of work. The petroleum industry literature deals more with evaluating the controlling factors in actual flood implementation. Surfactant loss has been broken down into adsorption, precipitation, and phase trapping. The effects of sacrificial agents, sulfonate fractionation, divalent ions, and salinity gradients all have been investigated. Since it is not the purpose of this paper to provide a review of the literature, we have attempted only to summarize some of this literature in the form of a table (see Table 1). Surfactant retention data have been presented in terms of a wide variety of units. These fall into two basic categories: molecules per unit area, which is indicative of surface coverage, and mass per unit of pore volume, which is indicative of surfactant consumption by the reservoir. We have chosen to express both our data and all of the data in Table 1 as microequivalents per square meter (µeq/m2) and milligrams active surfactant per milliliter of pore volume (mg AS/mL PV). In many cases this involved making assumptions as to rock density, porosity, surfactant equivalent weight, etc.; however, it has the advantage of allowing direct comparison of results.


2014 ◽  
Vol 2014 ◽  
pp. 1-12 ◽  
Author(s):  
Biji Shibulal ◽  
Saif N. Al-Bahry ◽  
Yahya M. Al-Wahaibi ◽  
Abdulkader E. Elshafie ◽  
Ali S. Al-Bemani ◽  
...  

Crude oil is the major source of energy worldwide being exploited as a source of economy, including Oman. As the price of crude oil increases and crude oil reserves collapse, exploitation of oil resources in mature reservoirs is essential for meeting future energy demands. As conventional recovery methods currently used have become less efficient for the needs, there is a continuous demand of developing a new technology which helps in the upgradation of heavy crude oil. Microbial enhanced oil recovery (MEOR) is an important tertiary oil recovery method which is cost-effective and eco-friendly technology to drive the residual oil trapped in the reservoirs. The potential of microorganisms to degrade heavy crude oil to reduce viscosity is considered to be very effective in MEOR. Earlier studies of MEOR (1950s) were based on three broad areas: injection, dispersion, and propagation of microorganisms in petroleum reservoirs; selective degradation of oil components to improve flow characteristics; and production of metabolites by microorganisms and their effects. Since thermophilic spore-forming bacteria can thrive in very extreme conditions in oil reservoirs, they are the most suitable organisms for the purpose. This paper contains the review of work done with thermophilic spore-forming bacteria by different researchers.


2009 ◽  
Vol 12 (05) ◽  
pp. 713-723 ◽  
Author(s):  
Adam Flaaten ◽  
Quoc P. Nguyen ◽  
Gary A. Pope ◽  
Jieyuan Zhang

Summary We present a systematic study of laboratory tests of alternative chemical formulations for a chemical flood design and application. Aqueous and microemulsion phase behavior tests have previously been shown to be a rapid, inexpensive, and highly effective means to select the best chemicals and minimize the need for relatively expensive coreflood tests. Microemulsion phase behavior testing was therefore conducted using various combinations of surfactants, cosolvents, and alkalis with a particular crude oil and in reservoir conditions of interest. Branched alcohol propoxy sulfates and internal olefin sulfonates showed high performance in these tests, even when mixed with both conventional and novel alkali agents. Systematic screening methods helped tailor and fine tune chemical mixtures to perform well under the given design constraints. The best chemical formulations were validated in coreflood experiments, and compared in terms of both oil recovery and surfactant retention in cores. Each of the four best formulations tested in corefloods gave nearly 100% oil recovery and very low surfactant adsorption. The two formulations with conventional and novel alkali agents gave almost zero surfactant retention. In standard practice, soft water must be used with alkali, but we show how alkali-surfactant-polymer (ASP) flooding can be used in this case even with very hard saline brine. Introduction Many mature reservoirs under waterflood have low economic production rates despite having as much as 50 to 75% of the original oil still in place. These reservoirs are viable candidates for chemical enhanced oil recovery (EOR) that uses both surfactant to reduce oil/water interfacial tension (IFT) and polymer to improve sweep efficiency. However, designing these aqueous chemical mixtures is complex and must be tailored to the reservoir rock and fluid (i.e., crude oil and formation brine) properties of the application. The early success of a systematic laboratory approach to low-cost, high performance chemical flooding depends on the efficiency of designing a formula for coreflood injection in accordance with sound evaluation criteria. A general, a three-stage procedure has been developed previously to screen hundreds of potential chemicals (i.e., surfactant, cosurfactant, cosolvent, alkali, polymer, and electrolytes), and arrive at a mixture having good recovery of residual oil in cores (Jackson 2006; Levitt 2006; Levitt et al. 2006). Additionally, furthering laboratory and field-testing in this area contributes to an expanding research database to help broaden reservoir types that can become candidates for routine chemical EOR application. This paper describes a systematic laboratory approach to low cost, high performance chemical flooding, and explores novel approaches to ASP flooding in reservoirs containing very hard saline brines. The design strategy first uses microemulsion phase behavior experiments to quickly select and optimize concentrations of injected chemicals. Assessment of formula optimization strategies are carried out through varying surfactant-to-cosurfactant ratio, reducing cosolvent concentration, reducing total surfactant concentration, selecting a suitable alkali, and using formation brine in the injection mixture. Formulations performing well in phase behavior are validated in coreflood experiments that adhere to necessary design criteria such as pressure and salinity gradients, surfactant adsorption, and capillary effects. We illustrate the application of our design approach in prepared Berea sandstone cores previously waterflooded with very hard saline brine, and show how ASP flooding can use some of the same brine in the chemical formulation. Conventional ASP flooding requires soft water that may not always be available, and softening hard brines can be very costly or infeasible in many cases depending on the location and other factors. These new results demonstrate high tolerance to both salinity and hardness of the high performance surfactants, and how novel alkalis--in particular sodium metaborate--can provide similar benefits in such harsh environments as sodium carbonate has shown in environments without divalent cations. This experimental success begins to vastly increase the range of conditions for economical EOR using chemicals.


2014 ◽  
Vol 5 (1) ◽  
pp. 73-91
Author(s):  
Mayadah Nayyef Shakir ◽  
Haidar Abdulaameer ◽  
Qussay Abed Hassan ◽  
Hussain Khalaf ◽  
Saad Saleh Jawad

This research aims to study the effect of using alkaline (caustic) and surfactant materials to improve the recovery of Iraqi crude oil under laboratory conditions. Flooding tests were carried out by using solutions of two alkalines (NaOH, Na2CO3) and two anionic surfactants materials were prepared at three concentrations ( 0.5%, 1%,  2 % )  using  sand  packs with ( 8.5 cm )  length  and   ( 6.5 cm ) diameter, which is saturated with tap water and then saturated with Basrah crude oil of 40 APIo density and 39.5 cp viscosity. The results were compared with the results of flooding tests by tap water and  2wt% brine water. In tests that tap water and 2wt% brine water were used as a primary recovery a secondary recovery had been tested by using materials that gave highest recovery, the results showed an increase in the recovery and the highest value was 50% by using 0.5% surfactant no.2.  The research showed different effects of these solutions. In general, alkalines type showed an increase in recovery factor vs. concentration, but surfactant type showed decrease in the recovery factor vs. concentration. Also, the results showed that the recovery by using surfactant no.2 were the best respective to other materials, and the highest recovery obtained was 90.9 at 0.5%.


1981 ◽  
Vol 21 (02) ◽  
pp. 218-228 ◽  
Author(s):  
Victor M. Ziegler ◽  
Lyman L. Handy

Abstract The effect of temperature on the adsorption of asulfonate surfactant and a nonionic surfactant ontocrushed Berea sandstone was studied by both staticand dynamic techniques. Static experiments were conducted over atemperature range from 25 to 95 degrees C to definetemperature-sensitive rock/surfactant systems and toestablish the shape of the equilibrium isotherm.Dynamic experiments served to reinforce the findingsof the static tests and extended the temperature rangefor sorption to 80 degrees C. This is a typicalsteamflood temperature. A mathematical model thatincorporates the mass transport, thermal degradation, and rate-dependent adsorption of the surfactantrepresented these dynamic results. The model wasused to determine the effect of temperature on the sorption rate constants. Mineral dissolution at elevated temperatures hasbeen found to cause precipitation of the sulfonate.Adsorption of the nonionic surfactant decreased withan increase in temperature at low concentrations, whereas the opposite was true at high concentrations.This has favorable implications for a low-concentration injection scheme. When performingstatic adsorption experiments, care had to be takenbecause of the poor thermal stability of the nonionic surfactant. Introduction Injection of surfactants concurrently with steam intooil-bearing reservoirs has been proposed recentlyto improve the recovery efficiency of the steam-driveprocess. From the behavior of chemical additivespreviously used in steamfloods, it is anticipated thatthe injected surfactant will travel through thatportion of the reservoir being flooded by hot water. Oil recovery can be increased if the surfactanteffectively reduces the residual oil saturation withinthis hot-water zone. For concurrent surfactant/steam injection to be technically attractive, a synergisticeffect between the surfactant and temperature isdesired. In our concept of the process, the surfactant mustmove in the heated portion of the reservoir and beable to function as an effective recovery agent atelevated temperatures for prolonged periods of time.Surfactant screening, therefore, requires thisinformation:surfactant stability under steamfloodconditions,temperature effects on the interfacial tension (IFT) between the reservoir oil and aqueoussurfactant,an evaluation of the effect oftemperature on surfactant flood performance, andthe effect of temperature on surfactant adsorption atthe water/solid interface. Handy et al. reported the thermal stabilities ofseveral classes of surfactants. Hill et al. showed thattemperature can have a dramatic effect in reducingthe IFT between crude oil and an aqueous sulfonatesystem. Handy et al. saw a similar temperatureeffect for a nonionic-surfactant/crude-oil system. Itappears, therefore, that the required synergismbetween temperature and surface activity necessaryfor concurrent surfactant/steam injection exists.Surfactant core floods are required to evaluate theeffect of temperature on oil recovery. Finally, toensure that the surfactant moves in the heatedportion of the reservoir, it is necessary to determinethe effect of temperature on adsorption. SPEJ P. 218^


SPE Journal ◽  
2016 ◽  
Vol 21 (04) ◽  
pp. 1164-1177 ◽  
Author(s):  
Yingcheng Li ◽  
Weidong Zhang ◽  
Bailing Kong ◽  
Maura Puerto ◽  
Xinning Bao ◽  
...  

Summary Test results indicate that a lipophilic surfactant can be designed by mixing both hydrophilic anionic and cationic surfactants, which broaden the design of novel surfactant methodology and application scope for conventional chemical enhanced-oil-recovery (EOR) methods. These mixtures produced ultralow critical micelle concentrations (CMCs), ultralow interfacial tension (IFT), and high oil solubilization that promote high tertiary oil recovery. Mixtures of anionic and cationic surfactants with molar excess of anionic surfactant for EOR applications in sandstone reservoirs are described in this study. Physical chemistry properties, such as surface tension, CMC, surface excess, and area per molecule of individual surfactants and their mixtures, were measured by the Wilhelmy (1863) plate method. Morphologies of surfactant solutions, both surfactant/polymer (SP) and alkaline/surfactant/polymer (ASP), were studied by cryogenic-transmission electron microscopy (Cryo-TEM). Phase behaviors were recorded by visual inspection including crossed polarizers at different surfactant concentrations and different temperatures. IFTs between normal octane, crude oil, and surfactant solution were measured by the spinning-drop-tensiometer method. Properties of IFT, viscosity, and thermal stability of surfactant, SP, and ASP solutions were also tested. Static adsorption on sandstone was measured at reservoir temperature. IFT was measured before and after multiple contact adsorptions to recognize the influence of adsorption on interfacial properties. Forced displacements were conducted by flooding with water, SP, and ASP. The coreflooding experiments were conducted with synthetic brine with approximately 5,000 ppm of total dissolved solids (TDS), and with a crude oil from a Sinopec reservoir.


1977 ◽  
Vol 17 (05) ◽  
pp. 337-344 ◽  
Author(s):  
F.J. Trogus ◽  
T. Sophany ◽  
R.S. Schechter ◽  
W.H. Wade

Abstract The adsorption of commercial polyoxyethylene nonyl phenols and alkyl benzene sulfonates was studied by measuring the surfactant breakthrough from Berea cores. A rate model that reduces to a Langmuir-type isotherm at equilibrium represented these dynamic results and predicted successfully the equilibrium isotherms determined by static experiments.The ratios of both adsorption and desorption were determined and were observed to increase with the number of ethylene oxide groups. Adsorption of the nonionic surfactant appeared to be by hydrogen bonding and the amount adsorbed per unit of area was the same on a number of metal oxide substrates.Negligible adsorption was observed for sulfonates with an alkyl chain length of 9 or less. Introduction Surfactant adsorption is one of the important features governing the economic viability of chemical flooding processes. However, the adsorption on mineral oxide surfaces is only one of several possible mechanisms leading to surfactant losses.Other mechanisms include precipitation of surfactant in the presence of divalent ions, diffusion of surfactant into dead-end pores, and surfactant partitioning into the oil phase. It is necessary partitioning into the oil phase. It is necessary to minimize the losses by all mechanisms. The work reported here addresses the problem of surfactant adsorption; other mechanisms are not considered.There are a number of approaches that have the potential for minimizing adsorption. The most potential for minimizing adsorption. The most desirable surfactant is one that does not adsorb at all; however, such surfactants may not be effective oil-recovery agents. Sacrificial agents that adsorb in place of the surfactant can be used in a preflush or as a competitive additive to the surfactant slug, but effective agents have not yet been identified.Two aspects of the adsorption process are of interest the rate and the amount adsorbed. Both are examined here. The measurements include the dynamic adsorption of both anionic and nonionic surfactants in Berea cores that are initially filled with brine. The breakthrough curves are represented successfully using a model that accounts for the surface coverage. The rate expression reduces to a Langmuir-type isotherm. The shape of this curve has been verified by conducting static experiments.The study included both nonionic and anionic surfactants. These were not pure surfactants but, in general, they are well characterized. The anionic surfactants were studied because their behavior should-be representative of more complex mixtures such as the petroleum sulfonates that have been regarded as prime candidates for oil-recovery agents. These sulfonates are sensitive to divalent ions and many chemical slugs include quantities of nonionic surfactants to alleviate this difficulty to some extent. Therefore, this study included a systematic study of a particular class of nonionic surfactants. This study is the first to report rates of adsorption and desorption. From this information, the nature of the adsorption can be better understood. THEORY Michaels and Morelos have established that the adsorption of polyanions on kaolin occurs by hydrogen bonding. The specific sites at which this adsorption takes place were not defined. For the adsorption of surfactants, this mechanism can be represented as follows: ....................... (1) SPEJ p. 337


SPE Journal ◽  
2008 ◽  
Vol 13 (02) ◽  
pp. 137-145 ◽  
Author(s):  
Kamlesh Kumar ◽  
Eric K. Dao ◽  
Kishore K. Mohanty

Summary Waterflooding recovers little oil from fractured carbonate reservoirs, if they are oil-wet or mixed-wet. Surfactant-aided gravity drainage has the potential to achieve significant oil recovery by wettability alteration and interfacial tension (IFT) reduction. The goal of this work is to investigate the mechanisms of wettability alteration by crude oil components and surfactants. Contact angles are measured on mineral plates treated with crude oils, crude oil components, and surfactants. Mineral surfaces are also studied by atomic force microscopy (AFM). Surfactant solution imbibition into parallel plates filled with a crude oil is investigated. Wettability of the plates is studied before and after imbibition. Results show that wettability is controlled by the adsorption of asphaltenes. Anionic surfactants can remove these adsorbed components from the mineral surface and induce preferential water wettability. Anionic surfactants studied can imbibe water into initially oil-wet parallel-plate assemblies faster than the cationic surfactant studied. Introduction Waterflooding is an effective method to improve oil recovery from reservoirs. For fractured reservoirs, waterflooding is effective only when water imbibes into the matrix spontaneously. If the matrix is oil-wet, the injected water displaces the oil only from the fractures. Water does not imbibe into the oil-wet matrix because of negative capillary pressure, resulting in very low oil recovery. Thus there is a need of tertiary or enhanced oil recovery techniques like surfactant flooding (Bragg et al. 1982; Kalpakci et al. 1990; Krumrine et al. 1982a; Krumrine et al. 1982b; Falls et al. 1992) to maximize production from such reservoirs. These techniques were developed in 1960s through 1980s for sandstone reservoirs, but were not widely applied because of low oil prices. Austad et al. (Austad and Milter 1997; Standnes and Austad 2000a; Standnes and Austad 2000b; Standnes and Austad 2003c) have recently demonstrated that surfactant flooding in chalk cores can change the wettability from oil-wet to water-wet conditions, thus leading to higher oil recovery (~70 % as compared to 5% when using pure brine). In 2003 (Standnes and Austad 2003a; Standnes and Austad 2003b; Strand et al. 2003), they identified cheap commercial cationic surfactants, C10NH2 and bioderivatives from the coconut palm termed Arquad and Dodigen (priced at US$ 3 per kg). These surfactants could recover 50 to 90% of oil in laboratory experiments. However, the cost involved is still high because of the required high concentration (~1 wt%) and thus there is a need to evaluate other surfactants. The advantage of using cationic surfactants for carbonates is that they have the same charge as the carbonate surfaces and thus have low adsorption. Nonionic surfactants and anionic surfactants have been tested by Chen et al. (2001) in both laboratory experiments and field pilots. Computed tomography scans revealed that surfactant imbibition was caused by countercurrent flow in the beginning and gravity-driven flow during the later stages. The basic idea behind these techniques is to alter wettability (from oil-wet to water-wet) and lower interfacial tension. Hirasaki and Zhang (2004) have studied different ethoxy and propoxy sulfates to achieve very low interfacial tension and alter wettability from oil-wet to intermediate-wet in laboratory experiments. The presence of Na2CO3 reduces the adsorption of anionic surfactant by lowering the zeta potential of calcite surfaces, and thus dilute anionic surfactant/alkali solution flooding seems to be very promising in recovering oil from oil-wet fractured carbonate reservoirs. It is very important to understand the mechanism of wettability alteration to design effective surfactant treatments and identify the components of oil responsible for making a surface oil-wet. It is postulated that oil is often produced in source rocks and then migrates into originally water-wet reservoirs. Some of the ionic/polar components of crude oil, mostly asphaltenes and resins, collect at the water/oil interface (Freer et al. 2003) and adsorb onto the mineral surface, thus rendering the surface oil-wet. In this work, we try to understand the nature of the adsorbed components by AFM. Recently, AFM has been used extensively to get the force-distance measurements between a tip and a surface. These force measurements can be used to calculate the surface energies using the Johnson-Kendall-Roberts (JKR), the Derjaguin-Muller-Toporov (DMT), and like theories (van der Vegte and Hadziioannou 1997; Schneider et al. 2003). AFM is also used extensively for imaging surfaces. It can be used in the contact mode for hard surfaces and in the tapping mode for soft surfaces. It can be used to image dry surfaces or wet surfaces; tapping mode in water is a relatively new technique. AFM images have been used to confirm the deposition of oil components on mineral surfaces (Buckley and Lord 2003; Toulhoat et al. 1994). In this work, crude-oil-treated mica surface is probed using atomic force microscopy before and after surfactant treatment to study the effects of surfactant. AFM measurements are correlated with contact-angle measurements. We also study surfactant solution imbibition into an initially oil-wet parallel plate assembly to relate wettability to oil recovery. Our experimental methodology is described in the next section, the results are discussed in the following section, and the conclusions are summarized in the last section.


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