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.     

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.     

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.     

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.     

Experimental and theoretical study for the determination of thermal conductivity of porous building material made with pumice and tragacanth

In this study, porous solid materials were produced with mixture combinations of materials such as tragacanth, cement, and pumice aggregate. Thermal conductivities of the produced materials were determined using hot wire methodology. The thermal conductivities of the produced samples ranged from 0.433 to 0.177 W/mK, depending on pumice diameter, pumice, tragacanth, and cement rates. A new model was developed to determine the effective thermal conductivities of the produced samples. The thermal conductivities obtained by the measurements were compared to the ones predicted by the model. The predicted values deviated as 1–31% from the measured values. It was finally shown that the experimental results were in good agreement to the predicted results.     

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。     

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.     

Experimental Study of Nanofluids Applied in EOR Processes

Nanoemulsions are small droplet-sized systems that have low surface tension and a small percentage of active material in their composition. In this study, low oil content nanoemulsion systems were developed for the use in enhanced oil recovery (EOR). The experiments were performed on a device capable of simulating petroleum reservoir conditions using sandstone rock cores. Nanoemulsions were obtained from a pre-selected microemulsion system composed of: RNX95 as surfactant, isopropyl alcohol as cosurfactant, kerosene as oil phase, and distilled water as aqueous phase. Different percentages of polyacrylamide were added to the systems obtained to evaluate the influence of viscosity in EOR results. The nanoemulsion droplet sizes ranged from 9.22 to 14.8 nm. Surface tension values were in the range of 33.6–39.7  dyn/cm. A nanoemulsion system with 2.5 wt% surfactant was used in EOR assays. The oil recovery was directly proportional to polymer percentage in the nanoemulsion, ranging from 39.6 to 76.8%. The total oil in the place recovery ranged from 74.5 to 90%.     

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.     

Palm-Based Nonionic Surfactants as Emulsifiers for High Internal Phase Emulsions

In the present study, a series of as-synthesized palm-based nonionic surfactants with various hydrophile–lipophile balance values were successfully synthesized. The critical micelle concentration and the Gibbs energy of the surfactants were determined and discussed. For the first time, the surfactants were used to stabilize three-component olein oil-in-water high internal phase emulsions, with an oil volume fraction of 0.85, and which were easily prepared by one-pot homogenization. Proof of high stability was confirmed by the satisfactory rheological profiles and further enhanced by a three-month storage exercise at an elevated temperature which showed no significant physical and rheological changes. These results suggest that low concentration of the surfactants efficiently stabilized the emulsions with high content of oil. Based on the optical micrograph observation, an average droplet size of less than 10 μm increased with increasing ethylene oxide chain length and temperature. The varying degree of viscosity resulted from the various ethylene oxide chain lengths of the surfactants. The hydration efficacy of the emulsions was examined in vivo using a corneometer. The impressive hydration efficacy of olein oil suggests that it could well be a potential moisturizing lipid which might interest dermatologists.     

Enhancing oil–solid and oil–water separation in heavy oil recovery by CO2-responsive surfactants

Interfacial properties are of critical importance to various separation applications. In heavy oil recovery, for example, a low oil–water interfacial tension (IFT) benefits the separation of heavy oil from their host rocks, which becomes problematic in the later stage of oil–water separation. CO₂-responsive surfactants were investigated to enhance the overall heavy oil recovery by switching their interfacial activity to the desired state in each stage. The surfactants at interfacially active state greatly enhanced the separation of heavy oil from hosting solids, as demonstrated by measuring contact angle and oil liberation using a custom-designed on-line visualization system. Meanwhile, the resulting heavy oil-in-water emulsions could also be easily demulsified by the bubbling of CO₂ gas, which switched off the interfacial activity of the surfactants. Furthermore, CO₂-responsive surfactants could be partially recycled in process water to improve sustainability, making CO₂-responsive surfactants to be promising chemical aids in heavy oil production and many other vital industries.     

Experimental study and mathematical model of nanoparticle transport in porous media

Two types of polysilicon nanoparticles (PN) were used in oil fields to improve oil recovery and enhance water injection respectively in this work. The physical properties of the nanoparticles were studied experimentally, and pore characteristics of sandstone were investigated by mercury injection experiments. The adsorption experiments of lipophobic and hydrophilic polysilicon nanoparticles (LHPN) were conducted to testify wettability change (from oil wetting to water wetting) of sandstone surface, and the nanoparticles attached to pore walls were observed by a transmission electron microscope (TEM). A mathematical model to describe the nanoparticles transport carried by two-phase flow in random porous media was presented and a numerical simulator was developed to simulate two application examples of the nanoparticles in oilfields. An important discovery is that water-phase permeabilities of these sandstones increase from 1.6 to 2.1 times of their original values. However, there are decreases in their absolute permeabilities because of nanoparticle adsorption on pore surfaces and nanoparticle capture at pore throats. The important parameters such as the distributions of porosities and permeabilities, the changes in water injection capability and oil recovery are obtained successfully by numerical simulation approach. Furthermore, the permeabilities obtained from numerical simulation have a good match with experimental data. The conclusion that polysilicon nanoparticles are effective agents for enhancing water injection capability or improving oil recovery can be safely drawn.     

聚合物微球提高低渗油藏渗吸效率微观实验研究

为了研究聚合物微球对低渗油藏渗吸采收率的作用效果,通过物理模拟实验和微观实验的方法分析了聚合物微球对剩余油的动用情况,研究了岩心自发渗吸的最佳效果。结果表明:带有聚合物微球的溶液与未加入聚合物微球的溶液相比对提高采收率起到了一定的作用,采收率在14%~15%,渗吸过程主要靠重力的作用凭借逆向渗吸的方式将原油置换出来。从微观实验可以看出聚合物微球对动用簇状剩余油有明显效果,对孔道进行了封堵,提高了渗吸液的波及体积,进而提高了采收率。     

Effect of a Spacer Group on Surface Activity, Salinity and Hardness Tolerance, Mimic Oil Washing Efficiency of Monododecyl Diaryl Disulfonate

Three anionic surfactants of the monododecyl diaryl disulfonate type (MDDADS-n, n = 0, 1, 2) were synthesized. The structural characters of MDDADS-n surfactants were verified by electrospray ionization/mass spectrometry. The effect of the spacer group on the surface activity, salinity and hardness tolerance and mimic oil washing efficiency were investigated. The results showed that the critical micelle concentration (CMC), surface tension at CMC, C₂₀ and the minimum area per molecule of the anionic surfactants increased when the spacer group length increased. There was less effect on mimic oil washing efficiency of MDDADS-n when the spacer group changed; meanwhile, they displayed higher mimic oil washing efficiency in salt solution (NaCl or CaCl₂) than that of sodium dodecylbenzenesulfonate (SDBS); all MDDADS-n surfactants showed much lower sensitivity to water hardness than SDBS, what would be beneficial to enhancing oil recovery in a high salinity oil field.     

Extended Surfactants Including an Alkoxylated Central Part Intermediate Producing a Gradual Polarity Transition—A Review of the Properties Used in Applications Such as Enhanced Oil Recovery and Polar Oil Solubilization in Microemulsions

The research published in the past half century indicates that surfactant interfacial performance in producing low tension or high solubilization with polar oils is not generally attained with pure conventional species exhibiting well-defined polar and nonpolar parts. The improvement trends reached with surfactant mixtures as well as the introduction of additives like cosurfactants and linkers lead to the introduction of the so-called extended surfactants, whose structure includes an intermediate polarity spacer between the hydrophilic head and the lipophilic tail. Recent investigations on different kinds of surfactants in a variety of applications—such as detergency, cosmetics, enhanced oil recovery or crude demulsifying, and vegetable oil extraction—indicate that these extended surfactants are likely to be particularly performing with oils containing polar groups, such as triacylglycerols and asphaltenic crudes. Possible applications of extended surfactants in enhanced oil recovery, crude emulsion breaking, detergency and cleaning, medicine and cosmetics vehicles, and natural oil extraction as well as some other cases are quickly reviewed.     

The performance of polymer solutions in enhanced oil recovery: studies on their rheological,interfacial, and porous media behaviors

Four polymeric solutions based on xanthan, high and low molecular weight sulfonated polyacrylamides, and hydrolyzed polyacrylamide were prepared in aqueous solutions and their behaviors in enhanced oil recovery applications were investigated. The effect of thermal aging on polymer solutions was evaluated through rheological measurement. Pendant drop method was also used for measuring the interfacial tension (IFT) between crude oil and brine containing different polymer solutions. Moreover, the zeta potential of the oil reservoir particles treated with oil and polymer was determined by electrophoresis method in a nano-zeta meter instrument. In addition, sand pack and core flooding setup were used for evaluating the effectiveness of the polymer solutions in porous media. Polymer solutions displayed non-Newtonian behavior in almost the whole range of the shear rate applied; a shear thinning behavior was seen. Furthermore, the aging of polymers in formation water decreased the shear viscosity of all the polymers. The oil/water IFT decreased by the addition of polymers to water. The effect of xanthan polymer on zeta potential value was greater than that of the three acrylamide-based polymers. According to sand pack tests, by increasing the polymer concentration, the incremental oil recovery initially increased up to a polymer concentration of 3,500 ppm and then started to fall. Recovery factor increased from 50 to 65 % using the polymer solution in core flooding experiments. By increasing the injection rate from 0.2 to 3 mL/min, the injected fluid had less time to sweep the pores and consequently the amount of recovered oil decreased.     

Mathematical modeling of gravity and buoyancy effect on low interfacial tension spontaneous imbibition in tight oil reservoirs

Considering capillary force, viscous force, and gravity and buoyancy effects due to the oil–water density difference during the imbibition process, a new mathematical model for core-scale spontaneous imbibition considering gravity and buoyancy is established. The imbibition rates with and without gravity and buoyancy in high-, low-, and ultralow-interfacial tension (IFT) solutions are compared. The study shows that oil buoyancy can accelerate the imbibition rate, and with increasing core permeability and decreasing IFT, the differences in imbibition rate with and without gravity and buoyancy become more significant. At a high IFT of dozens of mN/m, the gravity and buoyancy effects are nonsignificant and can be ignored, but at a low IFT such as at 0.355 mN/m and a core permeability above 1 mD, gravity and buoyancy must be considered in spontaneous imbibition simulations. In low-IFT solutions, the critical inverse Bond number when gravity and buoyancy must be considered is approximately 1 × 10⁻².     

双亲纳米SiO2颗粒的制备及提高渗吸采收率性能

以正辛基三乙氧基硅烷和3-巯基丙基三乙氧基硅烷为改性剂，以双氧水为氧化剂，在水基环境下对亲水纳米SiO2颗粒表面进行改性，得到具有磺酸基和辛基的双亲纳米SiO2颗粒，并通过红外和热重对其化学结构和热稳定性进行分析。将双亲纳米SiO2颗粒分散在地层水中制备纳米流体，并评价纳米流体的稳定性、界面性质和渗吸效率。利用核磁共振技术探究纳米流体渗吸过程中岩心孔隙内原油运移规律。结果表明，纳米流体储存30 d未出现分层现象，表现出良好的稳定性；经纳米流体处理的岩心亲水性增强。此外，双亲纳米SiO2颗粒将油水界面张力降低至1.7 mN/m；纳米流体渗吸采收率高达22.6%，渗吸初始阶段小孔隙中的原油被动用，而在渗吸后期阶段大孔隙中的原油才被动用。     

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.     

LC–MSMS analysis of acetamiprid residue in crude palm oil

A method for acetamiprid residue detection and quantification in crude palm oil (CPO) using LC–MSMS after the clean‐up with graphite packed SPE was developed. This method was validated in house and passed all important validation tests such as linearity, intermediate precision, and repeatability test. The limit of detection and quantification of the method were estimated from an acetamiprid standard calibration curve and the values were 4 and 10 ng/g, respectively. To examine the efficiency of the developed method, recovery experiment was carried out at the method limit of quantification using CPO, crude sunflower oil, crude rapeseed oil, and refined soybean oil. Results showed that this method was suitable for the analysis of acetamiprid residue in these oils with the recoveries ranged from 79 to 116%.