Pore-scale investigation of residual oil displacement in surfactant–polymer flooding using nuclear magnetic resonance experiments

Research on the Gangxi III area in the Dagang Oilfield shows that there was still a significant amount of oil remaining in oil reservoirs after many years of polymer flooding.This is a potential target for enhanced oil recovery（EOR）.Surfactant–polymer（SP） flooding is an effective chemical EOR method for mobilizing residual oil and improving displacement efficiency macroscopically,but the microscopic oil displacement efficiency in pores of different sizes is unclear.Nuclear magnetic resonance（NMR） is an efficient method for quantifying oil saturation in the rock matrix and analyzing pore structures.In this paper,the threshold values of different pore sizes were established from the relationship between mercury injection curves and NMR T2 spectrums.The distribution and migration of residual oil in different flooding processes was evaluated by quantitatively analyzing the change of the relaxation time.The oil displaced from pores of different sizes after the water flood,polymer flood,and the SP flood was calculated,respectively.Experimental results indicate that（1） the residual oil in medium pores contributed the most to the incremental oil recovery for the SP flood,ranging from 40 % to 49 %,and small pores usually contributed ／30 %;（2） the residual oil after the SP flood was mainly distributed in small and medium pores;the residual oil in medium pores accounted for 47.3 %–54.7 %,while that trapped in small pores was 25.7 %–42.5 %.The residual oil in small and medium pores was the main target for EOR after the SP flood in oilfields.

Effects of pore structure on surfactant/polymer floodingbased enhanced oil recovery in conglomerate reservoirs

To understand the displacement characteristics and remaining oil displacement process by the surfactant/polymer(SP) flooding in cores with different pore structures, the effects of pore structure on the enhanced oil recovery of SP flooding was investigated at the pore, core and field scales through conducting experiments on natural core samples with three typical types of pore structures. First, the in-situ nuclear magnetic resonance core flooding test was carried out to capture the remaining oil variation features in the water flooding and SP flooding through these three types of cores. Subsequently, at the core scale, displacement characteristics and performances of water flooding and SP flooding in these three types of cores were evaluated based on the full-size core flooding tests. Finally, at the field scale, production characteristics of SP flooding in the bimodal sandstone reservoir and multimodal conglomerate reservoir were compared using the actual field production data. The results show: as the pore structure gets more and more complex, the water flooding performance gets poorer, but the incremental recovery factor by SP flooding gets higher;the SP flooding can enhance the producing degree of oil in 1-3 μm pores in the unimodal and bimodal core samples, while it produces largely oil in medium and large pores more than 3 μm in pore radius in the multimodal core sample. The core flooding test using full-size core sample demonstrates that the injection of SP solution can significantly raise up the displacement pressure of the multimodal core sample, and greatly enhance recovery factor by emulsifying the remaining oil and enlarging swept volume. Compared with the sandstone reservoir, the multimodal conglomerate reservoir is more prone to channeling. With proper profile control treatments to efficiently enlarge the microscopic and macroscopic swept volumes, SP flooding in the conglomerate reservoir can contribute to lower water cuts and longer effective durations.

An Experimental Study on Alkaline/Surfactant/Polymer Flooding Systems Using Natural Mixed Carboxylate

Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.

PREPARATION,IDENTIFICATION AND INTERFACIAL ACTIVITIES OF PETROLEUM CARBOXYLATE AS SURFACTANT FOR CHEMICAL FLOODING

Petroleum carboxylate that may be suitable for tertiary oil recovery have been produced inexpensively from the fractions of Daqing crude oil by a two step process.The feed stock was first oxidized in the vapor phase,followed by reaction of the oxidized products with sodium hydroxide.Dilute solutions of sodium carboxylates were produced and show ultralow(10^(-2)mN/m)interfacial tensions(IFTs)against a variety of hydrocarbons with a wide range of ACN(Alkane Carbon Number).Infrared spectroscopy was used to identify the functional groups in the oxidized and the saponified products.

A New Surfactant Flooding Model for Low Permeability Reservoirs

Surfactant as a successful Enhanced Oil Recovery (EOR) agent has been widely used in many mature reservoirs. This research focuses on the description of surfactant solution at low permeability condition. A new three-dimensional, two?phase, three-component surfactant simulator is presented. The simulator is based on the non-Darcy flow characteristics of surfactant flooding in the low permeability formations. The change of threshold pressure and influences of surfactant on convection, diffusion, adsorption, and retention, are all considered. A new equation for the calculation of surfactant adsorption is employed, which can significantly promote the matching degree between the mathematical model and field practice. The design of this new simulator is to help the decision-making in the reservoir engineering analysis of surfactant EOR projects, to face the challenge of the design of injection schemes, to assist the surfactant screening, to screen and assess laboratory and field data and their effect on the performance predictions, and to find the optimal methods of field development.

Gas channeling control with an in-situ smart surfactant gel during water-alternating-CO_(2) enhanced oil recovery

Undesirable gas channeling always occurs along the high-permeability layers in heterogeneous oil reservoirs during water-alternating-CO_(2)(WAG)flooding,and conventional polymer gels used for blocking the“channeling”paths usually suffer from either low injectivity or poor gelation control.Herein,we for the first time developed an in-situ high-pressure CO_(2)-triggered gel system based on a smart surfactant,N-erucamidopropyl-N,N-dimethylamine(UC22AMPM),which was introduced into the aqueous slugs to control gas channeling inWAG processes.The water-like,low-viscosity UC22AMPM brine solution can be thickened by high-pressure CO_(2) owing to the formation of wormlike micelles(WLMs),as well as their growth and shear-induced structure buildup under shear flow.The thickening power can be further potentiated by the generation of denser WLMs resulting from either surfactant concentration augmentation or a certain range of heating,and can be impaired via pressurization above the critical pressure of CO_(2) because of its soaring solvent power.Core flooding tests using heterogeneous cores demonstrated that gas channeling was alleviated by plugging of high-capacity channels due to the in-situ gelation of UC22AMPM slugs upon their reaction with the pre-or post-injected CO_(2) slugs under shear flow,thereupon driving chase fluids into unrecovered low-permeability areas and producing an 8.0% higher oil recovery factor than the conventional WAG mode.This smart surfactant enabled high injectivity and satisfactory gelation control,attributable to low initial viscosity and the combined properties of one component and CO_(2)-triggered gelation,respectively.This work could provide a guide towards designing gels for reducing CO_(2) spillover and reinforcing the CO_(2) sequestration effect during CO_(2) enhanced oil recovery processes.

Studying the effect of surfactant assisted low-salinity water flooding on clay-rich sandstones

Sandstone reservoirs often contain clay particles that can cause damage and reduce permeability during low-salinity water flooding.In this study,the effect of surfactants on fine migration in clay-rich sandstones and its impact on oil recovery was investigated.First,the impact of surfactants on interparticle forces in fine-matrix,fine-fine,and oil-matrix systems was modeled.The results showed that both CTAB(cetyltrimethyl ammonium bromide)and QS(quillaja saponin)cause EDL compaction,weakening the repulsive forces.However,SDS(sodium dodecyl sulfate)and TX(triton X-100)do not affect the EDL.Next,the effect of surfactants on IFT reduction and wettability alteration was experimentally investigated.All surfactants reduced IFT due to the surface excessive concentration mechanism.The wettability alteration experiment illustrated that although QS and CTAB compact EDL around oil and matrix particles leading to attraction force augmentation,they both alter wettability through adsorption on matrix and carboxylic groups present in crude oil,respectively.Surfactant aqueous solutions were then injected into various clay-rich sandstone sanpacks,which resulted in increased oil recovery.However,the mechanisms leading to enhanced oil recovery variedby surfactant type.CTAB increased recovery by 10%through IFT reduction and wettability alteration,while SDS and TX increased recovery by 12%and 9%,respectively,through wettability alteration and extreme fine migration.In contrast,partial fine migration in the QS flooding experiment reached a recovery increase of 18%.Permeability trends through experiments were also recorded.During CTAB injection,permeability did not reduce,while QS aqueous solution reduced rock permeability to 5 m D.SDS and TX reduced the magnitude of permeability to 2 m D.In conclusion,this study demonstrates that surfactants can effectively improve oil recovery in clay-rich sandstones by altering the interparticle forces,reducing IFT,and changing wettability.The results suggest that the type of surfactant used should be carefully selected to achieve the desired recovery increase without affecting the permeability of the reservoir.

Hybrid low salinity water and surfactant process for enhancing heavy oil recovery

Combining low salinity water (LSW) with surfactants has an enormous potential for enhancing oil recovery processes. However, there is no consensus about the mechanisms involved, in addition to the fact that several studies have been conducted in model systems, while experiments with rocks and reservoir fluids are scarce. This study presents a core-flooding experiment of LSW injection, with and without surfactant, using the core and heavy oil samples obtained from a sandstone reservoir in southeastern Mexico. The effluents and the crude oil obtained at each stage were analyzed. The study was complemented by tomographic analysis. The results revealed that LSW injection and hybrid process with surfactants obtained an increase of 11.4 percentage points in recovery factor. Various phenomena were caused by LSW flooding, such as changes in wettability and pH, ion exchange, mineral dissolution, detachment of fines and modification of the hydrocarbon profile. In the surfactant flooding, the reduction of interfacial tension and alteration of wettability were the main mechanisms involved. The findings of this work also showed that the conditions believed to be necessary for enhanced oil recovery with LSW, such as the presence of kaolinite or high acid number oil, are not relevant.

Characteristics and mechanism of smart fluid for sweep-controlling during CO_(2) flooding

A smart response fluid was designed and developed to overcome the challenges of gas channeling during CO_(2)flooding in low-permeability,tight oil reservoirs.The fluid is based on Gemini surfactant with self-assembly capabilities,and the tertiary amine group serves as the response component.The responsive characteristics and corresponding mechanism of the smart fluid during the interaction with CO_(2)/oil were studied,followed by the shear characteristics of the thickened aggregates obtained by the smart fluid responding to CO_(2).The temperature and salt resistance of the smart fluid and the aggregates were evaluated,and their feasibility and effectiveness in sweep-controlling during the CO_(2)flooding were confirmed.This research reveals:(1)Thickened aggregates could be assembled since the smart fluid interacted with CO_(2).When the mass fraction of the smart fluid ranged from 0.05%to 2.50%,the thickening ratio changed from 9 to 246,with viscosity reaching 13 to 3100 mPas.As a result,the sweep efficiency in low-permeability core models could be increased in our experiments.(2)When the smart fluid(0.5%to 1.0%)was exposed to simulated oil,the oil/fluid interfacial tension decreased to the level of 1×10^(-2)mN/m.Furthermore,the vesicle-like micelles in the smart fluid completely transformed into spherical micelles when the fluid was exposed to simulated oil with the saturation greater than 10%.As a result,the smart fluid could maintain low oil/fluid interfacial tension,and would not be thickened after oil exposure.(3)When the smart fluid interacted with CO_(2),the aggregates showed self-healing properties in terms of shear-thinning,static-thickening,and structural integrity after several shear-static cycles.Therefore,this fluid is safe to be placed in deep reservoirs.(4)The long-term temperature and salt resistance of the smart fluid and thickened aggregates have been confirmed.

Enhanced oil recovery by nonionic surfactants considering micellization, surface, and foaming properties

Surfactants for enhanced oil recovery are important to study due to their special characteristics like foam generation,lowering interfacial tension between oleic and aqueous phases,and wettability alteration of reservoir rock surfaces.Foam is a good mobility control agent in enhanced oil recovery for improving the mobility ratio.In the present work,the foaming behavior of three nonionic ethoxylated surfactants,namely Tergitol 15-S-7,Tergitol 15-S-9,and Tergitol 15-S-12,was studied experimentally.Among the surfactants,Tergitol 15-S-12 shows the highest foamability.The effect of Na Cl concentration and synthetic seawater on foaming behavior of the surfactants was investigated by the test-tube shaking method.The critical micelle concentrations of aqueous solutions of the different nonionic surfactants were measured at 300 K.It was found that the critical micelle concentrations of all surfactants also increased with increasing ethylene oxide number.Dynamic light scattering experiments were performed to investigate the micelle sizes of the surfactants at their respective critical micelle concentrations.Core flooding experiments were carried out in sand packs using the surfactant solutions.It was found tha t22% additional oil was recovered in the case of all the surfactants over secondary water flooding.Tergitol 15-S-12exhibited the maximum additional oil recovery which is more than 26%after water injection.

A review of fluid displacement mechanisms in surfactant-based chemical enhanced oil recovery processes:Analyses of key influencing factors

Surfactant-based oil recovery processes are employed to lower the interfacial tension in immiscible displacement processes,change the wettability of rock to a more water-wet system and emulsify the oil to displace it in subsurface porous media.Furthermore,these phenomena can reduce the capillary pressure and enhance spontaneous imbibition.The key factors affecting such immiscible displacement process are temperature,salinity and p H of the fluids,surfactant concentration and adsorption.Therefore,before any surfactant flooding process is applied,extensive studies of fluid-fluid and rock-fluid interactions are needed.The use of other chemicals along with surfactants in chemical enhanced oil recovery(c EOR)processes have been widely considered to exploit the synergy of individual chemicals and complement the weakness arises from each of them during immiscible displacement of fluids in porous media.Therefore,such combinations of chemicals lead to alkaline-surfactant(AS),surfactantpolymer(SP),alkaline-surfactant-polymer(ASP),and nanoparticle-surfactant(NS)flooding processes,among others.In this review study,we categorised the role and displacement mechanisms of surfactants and discussed the key factors to be considered for analysing the fluid displacement in porous media.

Characteristics and displacement mechanisms of the dispersed particle gel soft heterogeneous compound flooding system

Considering high temperature and high salinity in the reservoirs, a dispersed particle gel soft heterogeneous compound(SHC) flooding system was prepared to improve the micro-profile control and displacement efficiency. The characteristics and displacement mechanisms of the system were investigated via core flow tests and visual simulation experiments. The SHC flooding system composed of DPG particles and surfactants was suitable for the reservoirs with the temperature of 80-110 °C and the salinity of 1×10~4-10×10~4 mg/L. The system presented good characteristics: low viscosity, weak negatively charged, temperature and salinity resistance, particles aggregation capacity, wettability alteration on oil wet surface, wettability weaken on water wet surface, and interfacial tension(IFT) still less than 1×10^(-1) mN/m after aging at high temperature. The SHC flooding system achieved the micro-profile control by entering formations deeply and the better performance was found in the formation with the higher permeability difference existing between the layers, which suggested that the flooding system was superior to the surfactants, DPG particles, and polymer/surfactant compound flooding systems. The system could effectively enhance the micro-profile control in porous media through four behaviors, including direct plugging, bridging, adsorption, and retention. Moreover, the surfactant in the system magnified the deep migration capability and oil displacement capacity of the SHC flooding system, and the impact was strengthened through the mechanisms of improved displacement capacity, synergistic emulsification, enhanced wettability alteration ability and coalescence of oil belts. The synergistic effect of the two components of SHC flooding system improved oil displacement efficiency and subsequently enhanced oil recovery.

Study of the Chemical Flooding Effect in Gao-63 Reservoir

This article is aimed to discuss the impact of using two different kinds of surfactant in enhancing oil recovery in heterogeneous reservoirs. With the background of Jidong oilfield, Rui Feng surfactant which could reach ultra-low interracial tension and combination surfactant RZ-JD80 with strong emulsifying property are chosen to do oil displacement and profile control-oil displacement experiment in homogeneous core and heterogeneous core respectively. The experiment is aimed to study the effect of oil displacement by injecting surfactant individually and the effect after injecting different profile control agent slug before surfactant flooding in heterogeneous cores. The results suggest that injecting Rui Feng surfactant and RZ-JD80 individually could enhance the oil displacement efficiency about 15 percentage points for homogeneous core. For strongly heterogeneous core, it is low efficiency by using either of these two surfactants individually. However, if injected a very little profile control agent slug before surfactant flooding, both of these two kinds of surfactant could enhance the oil recovery by different degree, especially, polymer microsphere plugging^RZ-JD80 flooding composite technology is more adaptable to Gao-63 reservoir. This technology could increase the recovery by 18.52 percentage points aRer surfactant flooding.

New insights into the mechanism of surfactant enhanced oil recovery:Micellar solubilization and in-situ emulsification

Reducing the oil-water interfacial tension(IFT)to ultra-low is believed the primary mechanism for surfactant-based enhanced oil recovery(EOR)process.However,field trials have shown that low concentration surfactant flooding can also improve oil recovery without ultra-low IFT.To clarify the mechanism behind,the currently-used surfactant,naphthenic arylsulfonate(NAS),was used to unravel its function during surfactant flooding from the horizon of micron-and nano-scale.The solubilization capacity of NAS micelle to petroleum fractions was evaluated through light absorbance strategy,smallangle neutron scattering,dynamic light scattering and transmission electron microscopy.It was found that micellar solubilization plays a significant role during the surfactant flooding.In-situ emulsification was visualized in microfluidics with three types of microchips,respectively.A series of displacement tests were carried out with NAS solution pumping into oil-saturated chip.The results show that in-situ emulsification improve oil recovery mainly through blocking and entrainment effects.Results from this work aid in understanding the interaction between surfactant solution and petroleum fractions at low surfactant concentration,which is helpful for design surfactant-based displacing system for EOR process.

Technologies of enhancing oil recovery by chemical flooding in Daqing Oilfield, NE China

By tracking and analyzing the research and practices of chemical flooding carried out in the Daqing Oilfield, NE China since the 1970 s, the chemical flooding theory, technology adaptability and existing problems were systematically summarized, and directions and ideas of development in the future were proposed. In enhanced oil recovery by chemical flooding, the Daqing Oilfield developed theories related to compatibility between crude oil and surfactant that may form ultra-low interfacial tensions with low-acidity oil, and a series of surfactant products were developed independently. The key technologies for chemical flooding such as injection parameter optimization and numerical simulation were established. The technologies of separation injection, cleansing and anti-scaling, preparation and injection, and produced liquid processing were developed. The matching technologies of production engineering and surface facilities were formed. Through implementation of chemical flooding, the Daqing Oilfield achieved outstanding performances with enhanced recovery rate of 12% in polymer flooding and with enhanced recovery rate of 18% in ASP flooding. To further enhance the oil recovery of chemical flooding, three aspects need to be studied:(1) fine characterization of reservoirs;(2) smart and efficient recovery enhancement technologies;(3) environment friendly, high-efficiency and smart matching processes.

分子动力学模拟表面活性剂驱油的研究进展与展望

表面活性剂在油田三次采油中具有广泛应用,从微观上对表面活性剂驱油的作用机理进行研究具有重要意义。近年来,分子动力学(Molecular Dynamics,MD)模拟已成为油气田开发研究的一种重要方法。运用MD模拟方法对表面活性剂进行研究已成为热点。通过MD模拟计算系统中所有运动粒子的牛顿方程数值解,分析原子位置随时间变化的规律。利用MD模拟研究表面活性剂分子的微观行为,从而探究表面活性剂分子的性能和微观驱油机理,MD模拟界面处表面活性剂的运动及聚集状态,分析界面处表面活性剂分子对界面体系的影响,对表面活性剂的现场应用具有一定的指导意义。为此,基于MD模拟的原理概述,首先对MD模拟中的力场、边界条件、系综类型和数值算法进行了总结;其次重点阐释了MD模拟表面活性剂驱油的微观机理,包括降低油水界面张力,改变表面润湿性,增加界面电荷及乳化作用等;介绍了MD模拟在表面活性剂驱油的应用实例;最后提出了MD模拟在表面活性剂驱油的发展方向,包括与生产相近的驱油环境、新型表面活性剂的设计、理论与实验的关系、分子力场和势能模型的优选、复合与多功能一体化表面活性剂的研发等。

DES+CTAB复配驱油剂体系提高低渗致密砂岩油藏采收率机理

针对低渗致密油藏注水困难、采收率低等问题,利用尿素基深共晶溶剂(DES)与十六烷基三甲基溴化铵(CTAB)复配的驱油剂体系,对驱油剂在低渗致密油藏中的降压增注和提高采收率机理进行了研究。研究结果表明:①驱油剂体系可以将油水界面张力降低至10^(-3)mN/m以下,大大提高了洗油效率;②驱油剂体系可有效抑制黏土矿物水化,避免了低渗致密砂岩中黏土矿物水化膨胀带来的流体敏感性损害;③驱油剂体系可对砂岩表面进行界面修饰,驱油剂溶液浸泡后样品的油相接触角由25.8°增加至61.4°,亲水性增强,亲油性减弱,有助于吸附在岩石孔隙壁面的油膜脱落;④超前注入驱油剂的注入压力降低率平均为79.64%,采收率平均为50.96%,远大于常规水驱(一次注水→注驱油剂驱→二次注水)的采收率。

砾岩油藏二元复合驱注入体系优化研究

新疆克拉玛依砾岩油藏经过几十年的水驱开发,面临剩余油高度分散、采油速度低等问题,选取聚合物部分水解聚丙烯酰胺(HPAM)和低张力表面活性剂PS-30及强乳化表面活性剂OP-10组合形成不同的二元复合体系,利用长砂管模型研究不同渗透率、不同驱替方式及不同注入量下复合驱体系在砾岩油藏的应用界限及提高采收率极限。实验结果表明:二元复合驱能够有效驱替残余油、扩大波及体积,显著提高砾岩油藏采收率。聚合物浓度为1000 mg/L,相对分子质量为7×10^(6)的聚合物在渗透率3×10^(-2)μm^(2)时复合驱采收率为66.31%,较水驱提高21.85个百分点。强乳化复合体系提高采收率效果好于低张力复合体系。复合体系注入量越高,提高采收率越大,但提高采收率幅度并非线性变化,复合体系注入量达到3.5 PV以后,复合体系提高采收率值逐渐趋于稳定,在注入10 PV后,复合驱体系最高提高采收率幅度达到40.38个百分点。

苏北盆地石港特低渗储层微观特征及提高采收率对策研究

苏北盆地石港油田属低孔、特低渗砂岩油藏,油井自然产能低,采用水力压裂后注水开发可提高产油能力,但油田开发中呈现低采油速度、低采出程度和开发效果差的特点,开发矛盾加剧。因此,需明确低效开发原因,探究提高采收率对策,为提高石港油田开发效果提供理论依据。通过全岩矿物成分分析、气测岩心孔渗参数、岩心敏感性评价等方法,从岩石矿物组成、孔喉结构和岩石敏感性等方面分析了其储层的微观特性;通过油藏数值模拟以及室内岩心实验研究了压裂水驱后剩余油的分布特征;通过核磁共振在线驱替实验探究了提高采收率的对策。结果显示,储层岩心呈现出典型的低孔、特低渗特征,且在开发过程中具有一定的速度敏感性和水敏感性。压裂水驱后,岩心中剩余油主要分布在0.01~1μm中小孔径的孔道中,使用表面活性剂驱及二次水驱将岩心中剩余油采收率提高了14.81%。储层渗透率特低、微孔隙和微裂缝发育、速敏、水敏等是其低效开发的主要原因。注水开发会导致岩石矿物膨胀、运移,增大流动阻力,所以区块经压裂水驱仅明显提高主流线上剩余油的采出程度,整体动用程度不高,剩余油仍有较多富集。建议采用化学驱及多轮次驱替以增强中小孔道中原油动用程度,进一步提升油田开发效果。

化学驱新技术及华北油田化学驱现状与展望

化学驱是大幅提升油田采收率的重要技术。化学驱理论和技术持续创新,应用规模不断扩大,其中聚合物驱矿场提高采收率约14%,二元复合驱和三元复合驱矿场提高采收率均在18%以上,纳米驱油技术预期采收率可达80%以上,中相微乳液驱表面活性剂体系性能不断突破,矿场取得良好增油效果。针对华北油田复杂断块砂岩油藏的实际情况,采用以可动凝胶为主的深部调驱技术,进一步提高了油田采收率。为进一步提高华北油田采收率,可以在深化油藏剩余油分布规律认识的基础上,加强基础理论研究,推动化学驱技术的持续创新和有序接替,配套开发化学驱地面工程,以期实现油田开发的可持续发展。