Surfactant Enhanced Oil Recovery in a High Temperature and High Salinity Carbonate Reservoir

The goal of this work was to find an effective surfactant system for enhanced oil recovery after water injection substituting for oil at a vuggy fractured reservoir with a high temperature and high salinity (220,000 mg/L). Four types of surfactants with concentrations (less than 0.2 %) were screened. Washing oil experiments were conducted in Amott cells. A surfactant system was established by mixing a surfactant with best ultimate recovery and one with best recovery rate. The optimized surfactant system could recover 50 % of remaining oil. To study the mechanism of enhanced oil recovery after water injection substituting oil, interfacial tension (IFT) and contact angle were measured. Experimental results showed that surfactants with good washing ability had low IFT, but surfactants with low IFT may not have a good washing ability. IFT had no obvious relationship with the increased oil recovery or washing ability. The optimized system could not alter carbonate to decrease the oil‐wetting capability. Though octadecyl trimethyl ammonium chloride had a good ability wet the carbonate with water, it could not recover much oil. Therefore, except for interfacial tension and wettability alteration, there must be other parameters dominating oil recovery after water injection substituting for oil.     

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.     

轮西缝洞型碳酸盐岩油藏注水替油工艺

轮西油藏为典型的缝洞型碳酸盐岩油藏。其储层特点、渗流模式与常规油藏不同,用常规注水方式来稳定地层压力和水驱油来提高采收率的方法难以奏效。为提高该类油藏的采收率,在分析轮西油藏缝洞单元内的油水关系及油井含水变化规律基础上提出单井注水替油工艺,给出了优选注水替油井、确定最佳注水时机及注水量的决策方法,并提出几点建议,为高效开发轮西油藏提供一种新方法。该工艺在LX10-H1井的实践结果表明：与未实施该工艺前相比较,油井关井时间由150天左右有效缩短至50~60天,而日产油量明显增加。     

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。     

Enhanced Wettability Alteration by Surfactants with Multiple Hydrophilic Moieties

The main production mechanism during water flooding of naturally fractured oil reservoirs is the spontaneous imbibition of water into matrix blocks and resultant displacement of oil into the fracture system. This is an efficient recovery process when the matrix is strongly water-wet. However, in mixed- to oil-wet reservoirs, secondary recovery from water flooding is often poor. Oil production can be improved by dissolving low concentrations of surfactants in the injected water. The surfactant alters the wettability of the reservoir rock, enhancing the spontaneous imbibition process. Our previous study revealed that the two main mechanisms responsible for the wettability alteration are ion-pair formation and adsorption of surfactant molecules through interactions with the adsorbed crude oil components on the rock surface. Based on the superior performance of surfactin, an anionic biosurfactant with two charged groups on the hydrophilic head, it was hypothesized that the wettability alteration process might be further improved through the use of dimeric or gemini surfactants, which have two hydrophilic head groups and two hydrophobic tails. We believe that when ion-pair formation is the dominant wettability alteration mechanism, wettability alteration in oil-wet cores can be improved by increasing the charge density on the head group(s) of the surfactant molecule since the ion-pair formation is driven by electrostatic interactions. At a concentration of 1.0 mmol L⁻¹ a representative anionic gemini surfactant showed oil recoveries of up to 49% original oil-in-place (OOIP) from oil-wet sandstone cores, compared to 6 and 27% for sodium laureth sulfate and surfactin, respectively. These observations are consistent with our hypothesis.     

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     

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.     

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.     

A New Series of Double-Chain Single-Head Sulfobetaine Surfactants Derived from 1,3-Dialkyl Glyceryl Ether for Reducing Crude Oil/Water Interfacial Tension

A new series of sulfobetaine surfactants with double-chain single-head structure were derived from 1,3-dialkyl glyceryl ethers and their performances in reducing Daqing crude oil/connate water interfacial tension (IFT) in the absence of alkali were studied. With a large hydrophilic head group and double hydrophobic chains, these surfactants are efficient at reducing crude oil/connate water IFT. Those with didecyl and dioctyl are good hydrophobic surfactants that can reduce Daqing crude oil/connate water to ultra-low IFT by mixing with a small molar fraction of various conventional single-chain hydrophilic surfactants, such as α-olefin sulfonates, dodecyl polyoxyethylene (10) ether, and cetyl dimethyl hydroxypropyl sulfobetaine. The asymmetric double-chain sulfobetaine derived from 1-decyl-3-hexyl glyceryl ether can reduce Daqing crude oil/connate water IFT to ultra-low solely over a wide concentration range (0.03–10 mM or 0.0017–0.58 wt.%), which allows for use of an individual surfactant instead of mixed surfactants to avoid chromatographic separation in the reservoir. In addition, formulations rich in sulfobetaine surfactants show low adsorption on sandstone, keeping the negatively charged solid surface water-wet, and forming crude oil-in-water emulsions. These new sulfobetaine surfactants are, therefore, good candidates for surfactant-polymer flooding free of alkali.     

Preparation and Performance Evaluation of Fatty Amine Polyoxyethylene Ether Diethyl Disulfonate for Enhanced Oil Recovery in High‐Temperature and High‐Salinity Reservoirs

To enhance oil recovery in high‐temperature and high‐salinity reservoirs, a novel fatty amine polyoxyethylene ether diethyl disulfonate (FPDD) surfactant with excellent interfacial properties was synthesized. The interfacial tension (IFT) and contact angle at high temperature and high salinity were systematically investigated using an interface tension meter and a contact angle meter. According to the experimental results, the IFT between crude oil and high‐salinity brine water could reach an ultra‐low value of 10^?3 mN m^?1 without the aid of extra alkali at 90°C after aging. The FPDD surfactant has strong wettability alternation ability that shifts wettability from oil‐wet to water‐wet. The FPDD surfactant with a high concentration also has good emulsion ability under high‐temperature and high‐salinity conditions. Through this research work, we expect to fill the lack of surfactants for high‐temperature and high‐salinity reservoirs and broaden its great potential application area in enhanced oil recovery.     

平面非均质油藏水气交替驱提高采收率室内实验研究

水气交替(WAG)驱提高采收率技术和应用研究在我国处于起步阶段。借助室内驱替实验,明确了WAG驱在平面非均质油藏的适应性及其提高采收率的作用机理。将并联式填砂管替代常规岩心夹持器,进一步减弱了长岩心驱替产生的末端效应和应力敏感现象,模拟真实的平面非均质油藏条件。实验结果表明,WAG驱可减缓气窜,改善吸水剖面。注入N2可加强三相分子之间的交换、扩散、渗吸作用。对于非均质性严重的储层,水气交替注入后水驱封堵高渗带,气驱驱扫小孔隙,帮助形成稳定的驱替前缘,提高低渗储层的驱油效率。     

Experimental Investigation into the Screening of New Surfactant Flowback Aids and Statistical Interpretation of Their Imbibing Capacity for Selected Core Substrates

Spontaneous imbibition is a pervasive part of many natural and industrial processes. As an inherent feature of fluid transport in porous media, it is a driver for oil recovery. Understanding spontaneous imbibition and leveraging surface science is fundamental for fluid recovery; specifically, the role of the surfactant in the imbibition processes and the potential to alter capillarity and wettability of reservoir rock. Surfactant success relies on the understanding of the factors governing the interfacial phenomena among crude oil, and formation properties under reservoir conditions. Developing a methodology coupling chemical performance with analytical techniques, and statistical interpretation of core/surfactant/oil interactions, can help establish workflows to advance new chemistries and enhance oil recovery. This article discusses a study of flowback aids formulated as microemulsions corresponding to the thermodynamically stable Winsor Type IV solutions. Neat formulated microemulsions, when dosed at field treatment concentrations, provide either oil-in-water droplet microemulsions or nanoemulsions. The solvency potential was measured, and the Kauri-butanol (Kb) value was determined. Parameters such as critical micelle concentration (CMC) and interfacial tension (IFT) were determined to characterize microemulsion solutions. These systems were tested using either in the column flow test with formation material sieved to match mineral grain size, or sandstone cores of various permeabilities. The results indicate that surfactant-based flow-enhancing aids are desirable for improved oil recovery when compared to the control fluid. The statistical analysis of core-fluid interaction includes an ANOVA followed by assumption evaluations and model interpretation, which demonstrates that the core permeability term, followed by the surfactant term, has the highest contribution whereas oil has no statistical significance to the model.     

高盐油藏提高采收率的室内研究

高盐油藏在水驱采油之后仍有相当一部分原油滞留在地层中,很难将其采出,因此可选用化学方法动用,但高盐油藏地层水矿化度相对较高,温度相对较高,普通表面活性剂很难满足如此苛刻条件下的油藏环境。因此需要将表面活性剂进行复配,充分发挥各种活性剂的优势,进而达到提高采收率的目的。针对玉门油田鸭儿峡L油藏地层水矿化度的特点,采用阴离子-两性表面活性剂复配,通过测定不同复配比和活性剂浓度下的油水界面张力,最终确定了适用于L油藏的表面活性剂驱油复配体系。实验表明在石油磺酸盐A与C14BE复配比为1:4、1:3,总浓度为0.6%、0.1%时,油水界面张力达到了10-3 m N/m级别。此驱油配方适用于L油藏提高采收率的要求。     

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.     

注水开发稠油生产井劈产方法研究

以多孔介质渗流力学、油气藏开发地质学、油藏精细描述技术、开发动态分析方法、流动单元、油田非均质对策论和油藏流场为基本理论基础,通过对注水开发方式生产的稠油油气藏所表现出的动态特征研究,首次提出了稠油生产井的劈产方法。在已经全面注水开发的稠油油气藏,将由应用该方法所得的计算结果与油藏特征再认识结论对比、综合分析,劈产分析可以揭示油气藏动态特征及其变化规律性,表明本方法可行、合理;本项工作的结果,不仅对实际稠油油气藏的动态分析具有重要意义,而且为注水开发稠油油气藏稳产高产技术的优化设计奠定了扎实的理论基础。     

Review on application of nanoparticles for EOR purposes: A critical review of the opportunities and challenges

Nanoparticles have already gained attentions for their countless potential applications in enhanced oil recovery.Nano-sized particles would help to recover trapped oil by several mechanisms including interfacial tension reduction, impulsive emulsion formation and wettability alteration of porous media. The presence of dispersed nanoparticles in injected fluids would enhance the recovery process through their movement towards oil–water interface. This would cause the interfacial tension to be reduced. In this research, the effects of different types of nanoparticles and different nanoparticle concentrations on EOR processes were investigated. Different flooding experiments were investigated to reveal enhancing oil recovery mechanisms. The results showed that nanoparticles have the ability to reduce the IFT as well as contact angle, making the solid surface to more water wet. As nanoparticle concentration increases more trapped oil was produced mainly due to wettability alteration to water wet and IFT reduction. However, pore blockage was also observed due to adsorption of nanoparticles, a phenomenon which caused the injection pressure to increase. Nonetheless, such higher injection pressure could displace some trapped oil in the small pore channels out of the model. The investigated results gave a clear indication that the EOR potential of nanoparticle fluid is significant.     

裂缝性低渗透碳酸盐岩脉冲注水实验研究

在裂缝性低渗透碳酸盐岩油藏,毛管自吸作用使润湿相进入喉道将原油从多孔基质岩块驱至裂缝,在油田开发中,采用脉冲注水方式和合理的开发参数能够有效的利用渗吸作用来改善该类油藏的水驱开发效果,有助于提高石油的采收率。本文通过大量的室内实验研究,分析碳酸盐岩岩芯自然渗吸规律和脉冲注水对注水驱油效果的影响,研究合理的注水参数。川中碳酸盐岩油藏基岩物性差,自然渗吸驱油效率低;脉冲注水比自然渗吸可提高驱油效率0．608～8．916个百分点,提高幅度与脉冲注水压力、注水周期和脉冲次数有关。研究成果对该类油藏合理注水开发方式具有参考作用。     

新型弱碱表面活性剂在三次采油中的应用

以α-烯烃为初始原料，经过烷基化，再经磺化、中和研制出了组分相对单一、结构合理的新型弱碱烷基苯磺酸盐表面活性剂。室内评价结果表明，该表面活性剂具有良好的界面活性，配制的复合体系在较宽的表面活性剂浓度和碱浓度范围可与原油形成10^-3mN／m数量级的超低界面张力。同时，该表面活性剂对大庆油田不同区块、不同油层的油水条件表现出了很强的适应性。另外，由于表面活性剂组成较为单一，可大大降低表面活性剂在地层中因吸附滞留而产生的色谱分离效应。室内天然岩心驱油实验表明，三元复合体系平均驱油效率可比水驱提高约20％。所开展的小井距三元复合驱矿场试验，取得了比水驱提高采收率24．66％的显著效果，为三元复合驱技术在大庆油田的工业化推广，特别是在二类油层的应用奠定了坚实基础。     

Impact of Divalent Ions on Heavy Oil Recovery by in situ Emulsification

Many reservoir formation brines are characterized by high salinity and contain high concentrations of divalent ions such as calcium, magnesium, and potassium. These challenging conditions can render the surfactants ineffective during chemical flooding for enhanced heavy oil recovery. Various brine types can have an impact on the stability of emulsions generated with chemicals as chemicals have various resistant levels toward hard divalent ions and salinities. To investigate the impact of brine hardness on heavy oil-in-water emulsion stability, glass tube experiments, microscopic visualization and sandpack flooding experiments, and Hele-Shaw visualization experiments were conducted in this study under low-salinity/hard-brine, high-salinity/hard-brine conditions using commercial chemicals, which are designed for specific reservoir brine conditions. Recovery results demonstrated that complex colloidal solution introduced in the previous study with silica and Dodecyltrimethylammonium bromide (DTAB) along with screened chemicals from glass tube tests in this study can enhance heavy oil recovery significantly with an addition of low concentration of xanthan gum (Lee and Babadagli 2018). The results confirmed the robustness of the complex colloidal solution formula to enhance oil recovery with low concentration of polymer under any reservoir brine conditions. The study also demonstrates the potential of polymer as an emulsion stabilization additive for enhanced heavy oil recovery by in situ emulsion generation. Polymer effects seemed to be particularly dominant under the low-salinity conditions than high-salinity conditions.     

Synthesis of an Alkyl Polyoxyethylene Ether Sulfonate Surfactant and Its Application in Surfactant Flooding

Surfactant flooding as a potential enhanced oil‐recovery technology in a high‐temperature and high‐salinity oil reservoir after water flooding has attracted extensive attention. In this study, the synthesis of an alkyl alcohol polyoxyethylene ether sulfonate surfactant (C₁₂EO₇S) with dodecyl alcohol polyoxyethylene ether and sodium 2‐chloroethanesulfonate monohydrate, and its adaptability in surfactant flooding were investigated. The fundamental parameters of C₁₂EO₇S were obtained via surface tension measurement. And the ability to reduce oil–water interfacial tension (IFT), wettability alteration, emulsification, and adsorption was determined. The results illustrated that IFT could be reduced to 10^?3 mN m^?1 at high temperature and high salinity without additional additives, and C₁₂EO₇S exhibited benign wettability alternate ability, and emulsifying ability. Furthermore, the oil‐displacement experiments showed that C₁₂EO₇S solution could remarkably enhance oil recovery by 16.19% without adding any additives.