Surfactant-Induced Wettability Alteration of Oil-Wet Sandstone Surface: Mechanisms and Its Effect on Oil Recovery

Different analytical methods were utilized to investigate the mechanisms for wettability alteration of oil-wet sandstone surfaces induced by different surfactants and the effect of reservoir wettability on oil recovery. The cationic surfactant cetyltrimethylammonium bromide (CTAB) is more effective than the nonionic surfactant octylphenol ethoxylate (TX-100) and the anionic surfactant sodium laureth sulfate (POE(1)) in altering the wettability of oil-wet sandstone surfaces. The cationic surfactant CTAB was able to desorb negatively charged carboxylates of crude oil from the solid surface in an irreversible way by the formation of ion pairs. For the nonionic surfactant TX-100 and the anionic surfactant POE(1), the wettability of oil-wet sandstone surfaces is changed by the adsorption of surfactants on the solid surface. The different surfactants were added into water to vary the core surface wettability, while maintaining a constant interfacial tension. The more water-wet core showed a higher oil recovery by spontaneous imbibition. The neutral wetting micromodel showed the highest oil recovery by waterflooding and the oil-wet model showed the maximum residual oil saturation among all the models.     

A new surfactant wettability alteration model for reservoir simulators

Surfactants enhance oil recovery in naturally-fractured oil-wet rocks by wettability alteration and interfacial tension reduction. The oil-wet state is ascribed to the adsorption of soap on the rock surface. Soaps are the dissociated forms of carboxylic acids in the crude oil, that is, carboxylate surfactants. This paper describes a new mechanistic surfactant wettability alteration model that was developed for and implemented in a reservoir simulator. The model captures the geochemical reactions of acid/soap, the formation of mixed micelles, Henry's law adsorption, and the formation of cationic surfactant-anionic soap ion-pairs. A new wettability scaling factor is used to interpolate between the oil-wet and water-wet relative permeability and capillary pressure curves. The new model also accounts for the effect of salinity and pH, so it should also be useful for modeling low-salinity flooding without surfactant. Previous surfactant wettability alteration models ignored the underlying mechanisms and were not predictive. Simulations of both static and dynamic imbibition were performed to better understand the key surfactant parameters and the dynamics of wettability alteration, microemulsion phase behavior, and interfacial tension reduction on oil recovery. Optimizing surfactant formulations for wettability alteration is discussed.     

Laboratory Studies to Determine Suitable Chemicals to Improve Oil Recovery from Garzan Oil Field

Garzan oil field is located at the south east of Turkey. It is a mature oil field and the reservoir is fractured carbonate reservoir. After producing about 1% original oil in place (OOIP) reservoir pressure started to decline. Waterflooding was started in order to support reservoir pressure and also to enhance oil production in 1960. Waterflooding improved the oil recovery but after years of flooding water breakthrough at the production wells was observed. This increased the water/oil ratio at the production wells. In order to enhance oil recovery again different techniques were investigated. Chemical enhanced oil recovery (EOR) methods are gaining attention all over the world for oil recovery. Surfactant injection is an effective way for interfacial tension (IFT) reduction and wettability reversal. In this study, 31 different types of chemicals were studied to specify the effects on oil production. This paper presents solubility of surfactants in brine, IFT and contact angle measurements, imbibition tests, and lastly core flooding experiments. Most of the chemicals were incompatible with Garzan formation water, which has high divalent ion concentration. In this case, the usage of 2-propanol as co-surfactant yielded successful results for stability of the selected chemical solutions. The results of the wettability test indicated that both tested cationic and anionic surfactants altered the wettability of the carbonate rock from oil-wet to intermediate-wet. The maximum oil recovery by imbibition test was reached when core was exposed 1-ethly ionic liquid after imbibition in formation water. Also, after core flooding test, it is concluded that considerable amount of oil can be recovered from Garzan reservoir by waterflooding alone if adverse effects of natural fractures could be eliminated.     

A Review of Gemini Surfactants: Potential Application in Enhanced Oil Recovery

Gemini surfactants are a group of novel surfactants with more than one hydrophilic head group and hydrophobic tail group linked by a spacer at or near the head groups. Unique properties of gemini surfactants, such as low critical micelle concentration, good water solubility, unusual micelle structures and aggregation behavior, high efficiency in reducing oil/water interfacial tension, and interesting rheological properties have attracted the attention of academic researchers and field experts. Rheological characterization and determination of the interfacial tension are two of the most important screening techniques for the evaluation and selection of chemicals for enhanced oil recovery (EOR). This review deals with rheology, wettability alteration, adsorption and interfacial properties of gemini surfactants and various factors affecting their performance. The review highlights the current research activities on the application of gemini surfactants in EOR.     

Enhanced oil recovery from high‐salinity reservoirs by cationic gemini surfactants

In order to enhance oil recovery from high‐salinity reservoirs, a series of cationic gemini surfactants with different hydrophobic tails were synthesized. The surfactants were characterized by elemental analysis, infrared spectroscopy, mass spectrometry, and ¹H‐NMR. According to the requirements of surfactants used in enhanced oil recovery technology, physicochemical properties including surface tension, critical micelle concentration (CMC), contact angle, oil/water interfacial tension, and compatibility with formation water were fully studied. All cationic gemini surfactants have significant impact on the wettability of the oil‐wet surface, and the contact angle decreased remarkably from 98° to 33° after adding the gemini surfactant BA‐14. Under the condition of solution salinity of 65,430 mg/L, the cationic gemini surfactant BA‐14 reduces the interfacial tension to 10^?3 mN/m. Other related tests, including salt tolerance, adsorption, and flooding experiments, have been done. The concentration of 0.1% BA‐14 remains transparent with 120 g/L salinity at 50 °C. The adsorption capacity of BA‐14 is 6.3–11.5 mg/g. The gemini surfactant BA‐14 can improve the oil displacement efficiency by 11.09%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46086.     

裂缝性致密油藏润湿性提高采收率技术研究

在裂缝性致密储层中,水驱效率往往由水自发吸入含原油基质块控制。当基质是原油润湿或中性润湿时,原油很难通过自发渗吸采出。研究目的是确定可以添加到注入水并提高深吸效率的表活剂组合。通过评价几种表活剂在储层温度和矿化度下的水稳定性并在富含粘土的砂岩上测量接触角,对储层岩心进行渗吸试验。结果表明使用一定浓度的表活剂溶液可实现矿物板的润湿反转。之后通过在致密油湿或中性润湿砂岩岩心上进行的自发吸入试验获得较润湿反转前68%的渗吸增量。同时数值模拟的研究也证实随着润湿性的变化,原油回收率也发生明显改变,且与断裂密度和原油粘度相关。     

Toward A Mechanistic Understanding of Re-Infiltration in Naturally Fractured Reservoirs with Surfactant-Aided Gravity Drainage Process

Surfactant-aided gravity drainage is an improved oil recovery technique for water-invaded zone in fractured carbonate reservoirs, which are mostly oil-wet or mixed-wet rocks. The re-infiltration mechanism in water-invaded zone has a considerable effect on oil vertical movement in gravity drainage processes. In this work, a mechanistic understanding of re-infiltration in surfactant-aided gravity drainage, in comparison to oil–water gravity drainage is presented using an experimentally and numerically validated model. A column model is constructed from three matrix blocks. These blocks are separated from each other by horizontal fractures. A storage tank is considered on top of the model to store depleted oil from matrix blocks. The stacked-blocks model for re-infiltration is validated and verified to simulate water and chemical flooding using a mesh independency study and experimental flooding data in a composite core experiment. Using this model, several analyses are performed to investigate effects of rock and fluid properties, rock saturation functions, wettability alteration, surfactant adsorption, and capillary continuity on re-infiltration.     

Mixing of Surfactin,an Anionic Biosurfactant,with Alkylbenzene Sulfonate,a Chemically Synthesized Anionic Surfactant,at the n-Decane/Water Interface

Biosurfactants show synergic effects with synthesized surfactant in reducing hydrophobic/hydrophilic interfacial tension, while the understanding of the synergistic mechanism is limited. In the present work, mixed monolayers of surfactin and branched alkylbenzene sulfonate at the n-decane/water interface were studied using atomistic molecular dynamics simulations, and the presence of surfactin affecting the microstructure and dynamic properties of the mixed monolayer was evaluated at molecular level. The density distributions of the surfactants along the direction normal to the interface, radial distribution functions of the surfactant head groups, hydrophobic contacts between surfactants, translational activities of both surfactants and counterions, and the dynamics of the hydrogen bonds formed between surfactant and water were calculated. The results suggested that the structure of the mixed monolayers was more compact than that of the individual system of alkylbenzene sulfonate and the interfacial tension was more efficiently reduced, and the translational activities of both surfactants within the mixed monolayers were much lower. The results implied that biosurfactant surfactin and alkylbenzene sulfonate mixed well at the n-decane/water interface, though they were both anionic surfactants.     

Experimental study of secondary and tertiary modes combined low salinity water and polymer flooding in sandstone porous media

Combined low salinity water (LSW) and polymer (LSP) flooding is the most attractive method of enhanced oil recovery (EOR). Considerable research has investigated effective mechanisms of LSP flooding. In this study, 10 laboratory core flood tests were carried out to evaluate the effects of LSW injection into samples without any clay particles, the timing of LSW injection, and the advantages of adding polymer to the injection water for EOR. Secondary and tertiary LSW injections were performed on sandpack samples with different wettability states and water salinity. Tertiary LSW injection after secondary synthetic seawater (SSW) injection in oil-wet samples resulted in 13% more oil recovery, while the water-wet sample showed no effect on the oil recovery. Secondary LSW injection in oil-wet porous media improved oil recovery by 8% of the original oil in place (OOIP) more than secondary SSW injection. Tertiary LSP flooding after secondary SSW injection in the oil-wet sample provided a recovery of 67.3% of OOIP, while secondary LSW injection followed by tertiary LSP flooding yielded the maximum ultimate oil recovery of about 77% of OOIP. The findings showed that the positive EOR effects of LSW and LSP flooding were the results of wettability alteration, pH increase, improved mobility ratio, better sweep efficiency, and oil redistribution. In addition, results showed that wettability alteration is possible without the presence of clay particles. The findings of this study can help for a better understanding of fluid propagation through the porous media and an investigation of delays in reaching ultimate oil recovery.     

Wettability alterations due to crude oil composition and an anionic surfactant in petroleum reservoirs

In this study, dual-drop dual-crystal (DDDC) contact-angle measurements have been made using dolomite rock and fluid samples from the Yates reservoir (West Texas) and in the presence of an anionic (ethoxy sulfate) surfactant. The experiments have been conducted at Yates reservoir conditions (4.8 MPa and 27.8°C) and using live synthetic oil to provide realistic measurements of in situ reservoir wettability. Stocktank crude oil has also been used at reservoir conditions to study the oil compositional effects on wettability. An advancing contact angle of 152° measured for Yates dolomite rock, stocktank oil and synthetic reservoir brine showed a strong oil-wet nature. However, experiments with Yates live synthetic oil resulted in an advancing contact angle of 55°, indicating a weakly water-wet behavior. In the rock-fluids system consisting of Yates stocktank oil, the surfactant altered the wettability to less oil-wet by decreasing the advancing contact angle to 135°. For rock-fluids system with Yates live synthetic oil, the surfactant altered the wettability from weakly water-wet to strongly oil-wet by increasing the advancing contact angle from 55° to 165°. The oil-wet behavior observed with Yates live synthetic oil due to the surfactant indicates a significant wettability altering capability of the surfactant.     

Progress in research of sulfobetaine surfactants used in tertiary oil recovery

The synthesis of sulfobetaine surfactants and their application in tertiary oil recovery (TOR) are summarized in this paper. The synthesis of sulfobetaine surfactants was classified into three categories of single hydrophobic chain sulfobetaine surfactants, double hydrophobic chain sulfobetaine surfactants and Gemini sulfobetaine surfactants for review. Their application in TOR was classified into surfactant flooding, microemulsion flooding, surfactant/polymer (SP) flooding and foam flooding for review. The sulfonated betaine surfactants have good temperature resistance and salt tolerance, low critical micelle concentration (cmc) and surface tension corresponding to critical micelle concentration (γ_cmc), good foaming properties and wettability, low absorption, ultralow interfacial tension of oil/water, and excellent compatibility with other surfactants and polymers. Sulfobetaine surfactants with ethoxyl structures, hydroxyl and unsaturated bonds, and Gemini sulfobetaine surfactants will become an important direction for tertiary oil recovery because they have better interfacial activity in high-temperature (≥90°C) and high-salinity (≥10⁴ mg/L) reservoirs. Some problems existing in the synthesis and practical application were also reviewed.     

A capillary bundle model for the forced imbibition in the shale matrix with dual-wettability

The forced imbibition during hydraulic fracturing is one of the main mechanisms of oil production in shale oil reservoirs. However, the shale matrix has complex structures of nanopores and is rich in organic matters. The wettability of nanopores in organics matters is different from the nanopores in inorganic matters, and the characteristic of dual-wettability leads to complex mechanisms of forced imbibition. This paper proposes a model for describing the imbibition in a dual-wettability shale oil reservoir based on the capillary tube model. The external displacement pressure gradient is also considered to study the forced and spontaneous imbibition of hydraulic fracturing liquid into oil-wet organic nanopores and water-wet inorganic nanopores. The slip effect in organic nanopores and the boundary-layer effect in inorganic nanopores are considered in this model. The analytical expressions for describing the location of the oil–water imbibition front in an oil-wet organic nanopore and a water-wet inorganic nanopore are derived, respectively. The semi-analytical solution for predicting flow rate in a shale core with an external pressure gradient is given and demonstrated with a case study.     

Investigation of Interfacial Tension Reduction,Wettability Alteration,and Oil Recovery Using a New Non-ionic Oil-Based Surfactant from Gemini Surfactants Family Coupled with Low-Salinity Water: Experimental Study on Oil-Wet Carbonate Rock

Low-salinity surfactant (LSS) flooding is a combined enhanced oil recovery (EOR) technique that increases oil recovery (OR) by altering the rock surface wettability and reducing oil–water interfacial tension (IFT). In this study, optimum concentrations of several types of salt in distilled water were obtained on the basis of IFT experiments for the preparation of low-salinity water (LSW). Then, a new oil-based natural surfactant (Gemini surfactant, GS) was combined with LSW to investigate their effects on IFT, wettability, and OR. Experimental results showed that LSW is capable of reducing IFT and contact angle, but the synergy of GS and the active ions Mg²⁺, Ca²⁺, and SO₄²⁻ in LSW was more effective on IFT reduction and wettability alteration. The combination of 1000 ppm MgSO₄ and 3000 ppm GS led to a decrease in contact angle from 134.82° to 36.98° (oil-wet to water-wet). Based on core flooding tests, LSW injection can increase OR up to 71.46% (for LSW with 1000 ppm MgSO₄), while the combination of GS and LSW, as LSS flooding, can improve OR up to 84.23% (for LSS with 1000 ppm MgSO₄ and 3000 ppm GS). Therefore GS has great potential to be used as a surfactant for EOR.     

Influence of Spacer Nature on the Aggregation Properties of Anionic Gemini Surfactants in Aqueous Solutions

A series of anionic gemini surfactants with the same structure except the spacer nature have been studied. Their solution properties were characterized by the equilibrium surface tension and intrinsic fluorescence quenching method. The critical micelle concentrations (CMC), surface tension at cmc, C₂₀, and the micelle aggregation number (N) were obtained. The surface tension measurements indicate that these gemini surfactants have much lower cmc values and great efficiency in lowering the surface tension of water compared with those of conventional monomeric surfactants. Furthermore, the standard free energy of micellization for anionic gemini surfactants was also determined. The results showed that the nature of the spacer has an important effect on the aggregation properties of gemini surfactants in aqueous solutions. The surfactant with a hydrophilic, flexible spacer was more readily able to form micelle compared with the surfactant with a hydrophobic, rigid spacer, which leads to a lower CMC value, larger N, more negative free energy of micellization, and a more closely packed micelle structure.     

Altering the wettability of bitumen-treated glass surfaces with ionic surfactants

The abilities of three ionic surfactants—sodium methylnaphthalene sulfonate (SMNS), sodium dodecyl sulfate (SDS), and cetyl trimethylammonium bromide (CTAB)—to alter the wettability of bitumen-treated glass surfaces was examined. Surface wettability was characterized by contact angles, and all measurements were carried out under alkaline conditions by having sodium carbonate (Na₂CO₃) dissolved in the aqueous phase. It was found that Na₂CO₃ alone could slightly increase the hydrophilcity of bitumen-treated glass surfaces. With surfactants added to the system, it was demonstrated that SMNS and SDS (both anionic surfactants) were much more effective in enhancing the water wettability of bitumen-treated glass in comparison to CTAB (a cationic surfactant). X-ray photoelectron spectroscopy (XPS) analyses were also conducted to determine the functional groups and relative mass concentrations of various elements on the glass substrates. Based on these results, we speculate that most or all of the adsorbed hydrocarbon material could be removed from a glass substrate through synergistic effects between sodium carbonate, which provides the alkaline condition, and anionic surfactants, which likely interacted with adsorbed cationic materials. This resulted in dramatic alteration in the wettability of bitumen-treated glass surfaces—from oil-wet to water-wet.     

Acidic Heavy Oil Recovery Using a New Formulated Surfactant Accompanying Alkali–Polymer in High Salinity Brines

The strength of a newly formulated surfactant with an alkali and polymer (AS/ASP) to improve an acidic heavy oil recovery was laboratory evaluated by various flooding experiments. The comparative role of the parameters like chemical nature, surface wettability, salinity, temperature and injection scheme were explored at high temperature and pressure on Berea sandstone rocks. According to the results the anionic surfactant is capable of providing proper oil displacement under high salinity conditions around 15 wt%. Continuous monitoring of differential pressure response and effluents’ state clearly represented the formation of an emulsified oil in high saline solutions with both alkali and surfactant. Adding sodium metaborate to the surfactant solution reduced the interfacial tension (IFT) to ultra low values and decreased the surfactant emulsion generation capability at higher salinities. Besides, adding Flopaam AN113SH to the chemical slug increased the residual oil removal owing to lower mobility ratios. So, while high capillary number and an emulsion phase were generated by the A/S slug phases, adding polymer could further enhance the performance of these chemicals. On the other hand, chemical flooding through the oil-wet medium resulted in shorter break through time, lower differential pressure, finer emulsion formation, and lower oil recovery in comparison to the similar water-wet cases.     

Superior enhancement of imbibition recovery by novel surfactant mixtures with a large hydrophobic group combined with nanosilica

Low interfacial tension (IFT) drainage and imbibition are effective methods for improving oil recovery from reservoirs that have low levels of oil or are tight (i.e., exhibit low oil permeability). It is critical to prepare a high efficient imbibition formula. In this work, a novel 2,4,6-tris(1-phenylethyl)phenoxy polyoxyethylene ether hydroxypropyl sodium sulfonate (TPHS) surfactant was synthesized and evaluated for imbibition. Its structure was confirmed by Fourier transform infrared spectroscopy and the interfacial tension (IFT) of the crude oil/0.07% TPHS solution was 0.276 mN/m. When 0.1 wt% TPHS was mixed with 0.2 wt% alpha olefin sulfonate (AOS), the IFT was lowered to 6 × 10⁻² mN/m. The synergy between nanoparticles (NPs) and TPHS/AOS mixed surfactant was studied by IFT, contact angle on sandstone substrates, zeta potential, and spreading dynamics through microscopic methods. The results show that the surfactant likely adsorbs to the NP surface and that NP addition can help the surfactant desorb crude oil from the glass surface. With the addition of 0.05 wt% SiO₂ NPs (SNPs), the imbibition oil recovery rate increased dramatically from 0.32%/h to 0.87%/h. The spontaneous imbibition recovery increased by 4.47% for original oil in place (OOIP). Compared to flooding by TPHS/AOS surfactant solutions, the oil recovery of forced imbibition in the sand-pack increased by 12.7% OOIP, and the water breakthrough time was delayed by 0.13 pore volumes (PV) when 0.05% SNPs were added. This paper paves the way for enhanced oil recovery in low-permeability sandstone reservoirs using novel TPHS/AOS surfactants and SNPs.     

纳米流体对储层润湿性反转提高石油采收率研究进展

储层岩石的润湿性对于石油采收率至关重要,近年来纳米流体润湿反转技术在提高石油采收率方面的应用得到了广泛关注,并取得了一系列成果。本文首先介绍了利用纳米流体对储层润湿性反转在提高石油采收率方面的应用,包括提高水驱效率和降压增注,其次归纳了润湿性变化的实验评价方法并分析影响纳米流体润湿反转效果的因素,表明纳米材料性质（类型、尺寸、浓度）和地层环境（温度、矿化度）均有不同程度的影响。然后阐述了纳米流体改变储层润湿性的机制,认为其包含纳米流体润湿铺展和纳米颗粒岩石壁面吸附的双重机制。最后指出运用此技术存在的问题和难点,并对以后的研究方向进行了展望。     

Progress in the Synthesis of Zwitterionic Gemini Surfactants

Zwitterionic gemini surfactants have hydrophilic head groups consisting of two polar groups with different charges. Species synthesized to date can be classed as anionic–cationic, anionic–nonionic, and cationic‐nonionic. These surfactants not only have a small repulsion between the hydrophilic head groups, but also have a more compact arrangement at the interface, which greatly reduces the surface and interfacial tensions. In addition, owing to the existence of zwitterions, they are endowed with a unique aggregation morphology and unique rheology in solution, so they has the potential for a number of applications. The present research situation and potential research directions of the synthesis methods of the three types of zwitterionic gemini surfactants are discussed in this paper.     

Characterizations of surfactant synthesized from Jatropha oil and its application in enhanced oil recovery

Surfactants are frequently used in chemical enhanced oil recovery (EOR) as it reduces the interfacial tension (IFT) to an ultra‐low value and also alter the wettability of oil‐wet rock, which are important mechanisms for EOR. However, most of the commercial surfactants used in chemical EOR are very expensive. In view of that an attempt has been made to synthesis an anionic surfactant from non‐edible Jatropha oil for its application in EOR. Synthesized surfactant was characterized by FTIR, NMR, dynamic light scattering, thermogravimeter analyser, FESEM, and EDX analysis. Thermal degradability study of the surfactant shows no significant loss till the conventional reservoir temperature. The ability of the surfactant for its use in chemical EOR has been tested by measuring its physicochemical properties, viz., reduction of surface tension, IFT and wettability alteration. The surfactant solution shows a surface tension value of 31.6 mN/m at its critical micelle concentration (CMC). An ultra‐low IFT of 0.0917 mN/m is obtained at CMC of surfactant solution, which is further reduced to 0.00108 mN/m at optimum salinity. The synthesized surfactant alters the oil‐wet quartz surface to water‐wet which favors enhanced recovery of oil. Flooding experiments were conducted with surfactant slugs with different concentrations. Encouraging results with additional recovery more than 25% of original oil in place above the conventional water flooding have been observed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2731–2741, 2017