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.     

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.     

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.     

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     

A Zwitterionic Surfactant Bearing Unsaturated Tail for Enhanced Oil Recovery in High‐Temperature High‐Salinity Reservoirs

High‐temperature/high‐salinity (HTHS) reservoirs contain a significant fraction of the world's remaining oil in place and are potential candidates for enhanced oil recovery (EOR). Selection of suitable surfactants for such reservoirs is a challenging task. In this work, two synthesized zwitterionic surfactants bearing a saturated and an unsaturated tail, namely 3‐(N‐stearamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate and 3‐(N‐oleamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate, respectively, were evaluated. The surfactant with the unsaturated tail showed excellent solubility in synthetic seawater (57,643 ppm) and in formation brine (213,734 ppm). However, the unsaturated surfactant with a saturated tail showed poor solubility, and therefore it was not evaluated further. The thermal stability of the synthesized unsaturated surfactant solution in seawater was evaluated by heating the solution at 90 °C in a sealed aging tube for 2 weeks. The thermal stability of the unsaturated surfactant was confirmed by FTIR and NMR analysis of the aged samples at such harsh conditions. The critical micelle concentration (CMC) of the synthesized unsaturated surfactant in seawater was 1.02 × 10^?4 mol L^?1, while the surface tension at CMC was 30 mN m^?1. The synthesized unsaturated surfactant was able to reduce the oil–water interfacial tension to ~10^?1 mN m^?1 at different conditions. A commercial copolymer of acrylamide and 2‐acrylamido‐2‐methylpropane sulfonic acid (AM‐AMPS) was tested for EOR applications in HTHS conditions. The addition of the synthesized unsaturated surfactant to the AM‐AMPS copolymer increased the viscosity of the system. The increase in oil recovery by injecting the unsaturated surfactant solution and the surfactant–polymer mixture in solution was 8 and 21%, respectively. The excellent properties of the synthesized unsaturated surfactant show that surfactants with an unsaturated tail can be an excellent choice for HTHS reservoirs.     

Novel fluorinated surfactants for enhanced oil recovery in carbonate reservoirs

Novel surfactant‐polymer (SP) formulations containing fluorinated amphoteric surfactant (surfactant‐A) and fluorinated anionic surfactant (surfactant‐B) with partially hydrolyzed polyacrylamide (HPAM) were evaluated for enhanced oil recovery applications in carbonate reservoirs. Thermal stability, rheological properties, interfacial tension, and adsorption on the mineral surface were measured. The effects of the surfactant type, surfactant concentration, temperature, and salinity on the rheological properties of the SP systems were examined. Both surfactants were found to be thermally stable at a high temperature (90 °C). Surfactant‐B decreased the viscosity and the storage modulus of the HPAM. Surfactant‐A had no influence on the rheological properties of the HPAM. Surfactant‐A showed complete solubility and thermal stability in seawater at 90 °C. Only surfactant‐A was used in adsorption, interfacial tension, and core flooding experiments, since surfactant‐B was not completely soluble in seawater and therefore was limited to deionized water. A decrease in oil/water interfacial tension (IFT) of almost one order of magnitude was observed when adding surfactant‐A. However, betaine‐based co‐surfactant reduced the IFT to 10^?3 mN/m. An adsorption isotherm showed that the maximum adsorption of surfactant‐A was 1 mg per g of rock. Core flooding experiments showed 42 % additional oil recovery using 2.5 g/L (2500 ppm) HPAM and 0.001 g/g (0.1 mass%) amphoteric surfactant at 90 °C.     

Model Development for MEOR Process in Conventional Non‐Fractured Reservoirs and Investigation of Physico‐Chemical Parameter Effects

A three‐dimensional multi‐component transport model in a two‐phase oil‐water system was developed. The model includes separated terms to account for the dispersion, convection, injection, growth and death of microbes, and accumulation. For the first time, effects of both wettability alteration of reservoir rock from oil wet to water wet and reduction in interfacial tension (IFT) simultaneously on relative permeability and capillary pressure curves were included in a MEOR simulation model. Transport equations were considered for the bacteria, nutrients, and metabolite (bio‐surfactant) in the matrix, reduced interfacial tension on phase trapping, surfactant and polymer adsorption, and effect of polymer viscosity on mobility of the aqueous phase. The model was used to simulate effects of physico‐chemical parameters, namely flooding time schedules, washing water flowrate, substrate concentration, permeability, polymer and salinity concentration on Original Oil In Place (OOIP) in a hypothetical reservoir.     

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.     

Viscoelastic Surfactants with High Salt Tolerance,Fast‐Dissolving Property,and Ultralow Interfacial Tension for Chemical Flooding in Offshore Oilfields

Injected chemical flooding systems with high salinity tolerance and fast‐dissolving performance are specially required for enhancing oil recovery in offshore oilfields. In this work, a new type of viscoelastic‐surfactant (VES) solution, which meets these criteria, was prepared by simply mixing the zwitterionic surfactant N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (HDPS) or N‐octyldecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (ODPS) with anionic surfactants such as sodium dodecyl sulfate (SDS). Various properties of the surfactant system, including viscoelasticity, dissolution properties, reduction of oil/water interfacial tension (IFT), and oil‐displacement efficiency of the mixed surfactant system, have been studied systematically. A rheology study proves that at high salinity, 0.73 wt.% HDPS/SDS‐ and 0.39 wt.% ODPS/SDS‐mixed surfactant systems formed worm‐like micelles with viscosity reaching 42.3 and 23.8 mPa s at a shear rate of 6 s^?1, respectively. Additionally, the HDPS/SDS and ODPS/SDS surfactant mixtures also exhibit a fast‐dissolving property (dissolution time <25 min) in brine. More importantly, those surfactant mixtures can significantly reduce the IFT of oil–water interfaces. As an example, the minimum of dynamic‐IFT (IFT_min) could reach 1.17 × 10^?2 mN m^?1 between the Bohai Oilfield crude oil and 0.39 wt.% ODPS/SDS solution. Another interesting finding is that polyelectrolytes such as sodium of polyepoxysuccinic acid can be used as a regulator for adjusting IFT_min to an ultralow level (<10^?2 mN m^?1). Taking advantage of the mobility control and reducing the oil/water IFT of those surfactant mixtures, the VES flooding demonstrates excellent oil‐displacement efficiency, which is close to that of polymer/surfactant flooding or polymer/surfactant/alkali flooding. Our work provides a new type of VES flooding system with excellent performances for chemical flooding in offshore oilfields.     

Salt-Induced Constructions of Gemini-like Surfactants at the Interface and Their Effects on the Interfacial Tension of a Water/Model Oil System

It is an urgent issue to enhance oil recovery for unconventional reservoirs with high salinity. Focused on this topic, salt addition is a powerful tool to motivate the surfactant assembly at the water/oil interface and improve the interfacial activity. We used a cationic surfactant cetyltrimethylammonium bromide (CTAB) and an anionic salt dicarboxylic acid sodium (CnDNa) to construct gemini-like surfactants at the interface and evaluated their ability to reduce the interfacial tension (IFT) between model oil (toluene and n-decane, v:v = 1:1) and water. Interestingly, the fabrication of a (CTAB)₂/C4DNa gemini-like surfactant was hardly achieved at the fresh water/model oil interface, but accomplished at the brine/model oil interface. At a high NaCl concentration (100,000 mg L⁻¹), the IFT value is reduced to 10⁻³ mN m⁻¹ order of magnitude, which is generally desired in practical applications. The control experiments displacing the surfactant type and the spacer length further confirmed the NaCl effects on the interfacial assembly.     

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.     

三次采油用耐温耐盐表面活性剂BHJ-2的研究

针对碳酸盐岩油藏具有高温、高矿化度的特点,研制出适合该类型油藏三次采油用耐温耐盐型表面活性剂BHJ-2。考察了其耐温耐盐性、界面活性、润湿性能、吸附性能、洗油效率、驱油效率等;结果表明,BHJ-2耐温达140℃,耐盐达23.3×104mg/L,吸附损失为0.574mg/g油砂,可将油-地层水-岩石接触角由亲油性109.6°转变为亲水性61.4°。在140℃高温条件下老化30d后,界面活性和洗油效率基本不变,油水界面张力为0.576mN/m,静态洗油效率达到83.7%,可提高驱替效率36.7%,研究表明BHJ-2可适用于高温高矿化度条件的亲油性碳酸盐岩油藏。     

三次采油用耐温耐盐表面活性剂BHJ-2的研究

针对碳酸盐岩油藏具有高温、高矿化度的特点,研制出适合该类型油藏三次采油用耐温耐盐型表面活性剂BHJ-2。考察了其耐温耐盐性、界面活性、润湿性能、吸附性能、洗油效率、驱油效率等;结果表明,BHJ-2耐温达140℃,耐盐达2.33×10~5mg/L,吸附损失为0.574 mg/g油砂,可将油-地层水-岩石接触角由亲油性109.6°转变为亲水性61.4°。在140℃高温条件下老化30 d后,界面活性和洗油效率基本不变,油水界面张力为0.576 m N/m,静态洗油效率达到83.7%,可提高驱替效率36.7%,研究表明,BHJ-2可适用于高温高矿化度条件的亲油性碳酸盐岩油藏。     

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.     

Performance of sea water dilution on the surface free energies of the crude oils in water-flooded carbonate rock

Although several investigations have studied the low-salinity water injection (LSWI) performance during the past decades, the effect of crude oil type on the interfacial tension (IFT) and wettability alteration is still in dark. In this regard, this study is aimed to obtain the thermodynamic energies including adhesion, cohesion and spreading coefficient during LSWI. To achieve this goal, IFT and static contact angle values of three different crude oils (i.e. light, medium and heavy) are measured as a function of sea water salinity. The obtained results revealed that the dilution of sea water can change the wettability of reservoir rock from oil wet state towards water wet state, while crude oil type implies no significant effect on the wettability alteration. Besides, the results illustrated that although the dilution of sea water unfavorably changed the IFT of light and heavy crude oils, it could favorably change the spreading coefficient.     

A Star-Shaped Anionic Surfactant: Synthesis,Alkalinity Resistance,Interfacial Tension and Emulsification Properties at the Crude Oil–Water Interface

In this research, a star‐shaped surfactant was synthesized through the chlorination reaction, alkylation reaction and sulfonation reaction of triethanolamine, which is composed of three hydrophobic chains and three sulfonate hydrophilic groups. The critical micelle concentration (CMC) of the surfactant was measured by the surface tension method, and the results showed that it had high surface activity with CMC of 5.53 × 10^?5 mol/L. The surfactant was superior in surface active properties to the reference surfactants SDBS and DADS‐C₁₂. The interfacial tension (IFT) of the studied crude oil–water system (surfactant concentration 0.1 g/L, NaOH concentration 0.5 g/L, and experimental temperature 50 °C) dropped to 1.1 × 10^?4 mN/m, which can fulfil the requirement of surfactants for oil displacement. An aqueous solution of the surfactant and crude oil was emulsified by shaking, which formed a highly stable oil‐in‐water (O/W) emulsion with particle size of 5–20 μm. The oil displacement effect was almost 12%.     

From Phase Behavior to Understand the Dominant Mechanism of Alkali-Surfactant-Polymer Flooding in Enhancing Heavy Oil Recovery

The primary objective of this work was to understand the dominant mechanism(s) of alkali‐surfactant‐polymer (ASP) flooding in enhancing heavy oil recovery. Chemical formulations were first optimized based on phase behavior studies. The data indicated that alkali and surfactant created a synergistic effect at the oil/water interface, which further decreased the interfacial tension (IFT) and improved the emulsification. However, it was also found that the addition of alkali was detrimental to the viscous properties of the chemical systems and caused the ultimate oil recovery to decrease. In other words, the macroscopic sweep efficiency as a result of viscosity was the primary factor determining the overall recovery of heavy oil followed by emulsification, which was verified by the phase behavior of the effluent. Based on the experimental results, we found that for this targeted heavy oil reservoir, surfactant‐polymer (SP) flooding was more appropriate than ASP flooding and it was not necessary to decrease the IFT to the ultralow level (10^?3 mN/m) using alkali. Through chemical flooding, the incremental oil recovery was increased up to 27% of original oil in place, indicating the potential of this technique in heavy oil reservoirs.     

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。     

Synergy between Sugar-Based Anionic-Nonionic Surfactants and Ag-TiO2 Nanohybrids for Enhanced Oil Recovery

For improving the oil recovery performance, Ag-TiO₂ nanoparticles (NP) were added to the eco-friendly sugar-based anionic nonionic surfactant (GDA) solution, and the mixtures acted as the oil displacement agent. The synthesized GDA and Ag-TiO₂ were characterized using Fourier transform infrared spectrometry (FT-IR), ¹H nuclear magnetic resonance (¹H NMR), and X-ray diffraction (XRD). Changes in the zeta potential and transmission electron microscope (TEM) images of the mixtures confirmed their synergistic effects on the suspension stability. The relationships between surface tension, interfacial tension (IFT), three-phase contact angle, and emulsion and oil recovery efficiency were comprehensively investigated, both before and after Ag-TiO₂ NP addition. We concluded that the Ag-TiO₂/GDA mixtures could effectively alter the contact angle, decrease IFT, and form stable emulsions, thereby resulting in the enhancement of oil recovery. The core flooding conducted with the stabilized NP-surfactant (Ag-TiO₂ and GDA) fluid showed a marked improvement in oil recovery over 18%. This study provides additional options for using the synergistic effect of NP and surfactants for enhanced oil recovery.     

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.