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.     

Laboratory Study on the Oil Displacement Properties of Sugar Amine Sulfonate Surfactant

A sugar amine sulfonate surfactant (SAS) was used to enhance oil recovery by chemical flooding. The interfacial tension between an SAS solution and four kinds of crude oil was determined. Oil (4) containing the largest amount of medium chain length components was the most suitable candidate because the IFT could be reduced to an ultralow range (10^?3 mN/m) at optimum NaCl concentration. Emulsions consisting of oil (4) and SAS solution and the adsorption density of SAS on sandstone were studied. Compared with A37 (alkyl ether sulfate), SAS ws able to form more stable emulsions and the adsorption density was equivalent in the typical concentration range of chemical flooding. Both SAS and A37 adsorption data on sandstone followed the Langmuir isotherm model. SAS increased the apparent viscosity of KY-1500 (modified polyacrylamide) in a low concentration range and improve the viscoelasticity. A combination of SAS and KY-1500 (SP) enhanced oil recovery by 16.05 versus 14.31% (using KY-1500 alone).     

新型两性表面活性剂的驱油体系界面特性变化规律研究

随着三次采油技术的不断发展,复合体系的表面活性性能和含量是在提高采收率技术研究中日趋重要。本文针对新型两性表面活性剂一元及聚合物/表面活性剂二元体系同油的界面特性展开了研究。结果表明：一元体系中表面活性剂质量浓度越高,界面张力达到稳定所需时间越短;随着体系中表面活性剂质量浓度的增加,稳定界面张力值越低。聚合物对两性表面活性剂同模拟油之间的界面张力有影响,且有利于体系同模拟油间的界面张力的降低;但界面张力并不是随着聚合物质量浓度的增加一直单纯降低,当质量浓度为1.0g/L时界面张力最低。     

Adsorption of surfactant during chemical enhanced oil recovery

Surfactant is extensively used as chemicals during chemical enhanced oil recovery (CEOR) process. Effectiveness of surfactant CEOR process depends on several parameters like formation of micro emulsion, ultra-low interfacial tension (IFT) and adsorption of surfactant. First two parameters enhance the effectiveness while the last parameter reduces the effectiveness. Micro emulsions are highly desirable for CEOR due to its low interfacial tension (IFT) value and higher viscosity. In this research the size of the emulsions were studied with particle size analyzer to study the liquid–liquid absorption process and the entrapment of oil drops inside surfactant drop. Initially, the average surfactant drop size was found to be 100 nm, after mixing the surfactant slug with reservoir crude, the size was increase up to 10 times. It signifies the formation of micro emulsion between surfactant and oil. Another attempt was done in this research to study the adsorption mechanism of surfactant on reservoir rock. The process of adsorption was studied by Langmuir and Freundlich isotherm to understand the adsorption phenomena. In this study, it was found that the adsorption follows Freundlich isotherm and the adsorption phenomena was chemical for surfactant flooding process. In chemical adsorption phenomena, the rate of adsorption is high because, surfactant molecules are adsorbed layer after layer by the rock surface. Use of alkali along with surfactant reduces adsorption of surfactant since, alkali blocked the active clay sites before interacting with surfactant and hence the adsorption isotherm was found to be Langmuir and phenomena was physical adsorption.     

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.     

表面活性剂同系物体系对原油界面张力的影响

分别从表面活性剂的亲油性和亲水性的二种性能 ,研究了复配型表面活性剂的性能及规律。在表面活性剂同系物复配的研究中 ,得出相对分子质量分布窄的表面活性剂不能与原油形成低的界面张力 ,但两种以上相对分子质量分布窄的表面活性剂按一定比例混合后 ,则可以与大庆原油形成超低界面张力。形成超低界面张力的表面活性剂平均当量范围为 410～ 430 ,相对分子质量、碱浓度和界面张力三者之间有一定规律 ,即表面活性剂平均相对分子质量增加 ,界面张力曲线向低浓度碱方向移动 ;平均相对分子质量降低 ,界面张力曲线向高浓度碱方向移动。相对分子质量分布是影响界面张力的又一因素 ,表面活性剂相对分子质量分布、原油中的碳数分布和界面张力可能存在某种特定联系。支链对降低界面张力方面比直链有更好的效果 ,表面活性剂相对分子质量越高 ,则油砂对其吸附量越大     

Intrinsic viscosity,rheological property,and oil displacement of hydrophobically associating fluorinated polyacrylamide

The surface‐active polymer (FPAM) was synthesized by free‐radical polymerization of acrylamide (AM), 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and N ‐dodecyl‐N ‐perfluoro octane sulfonyl acrylamide (AMPD), which was prior prepared by reacting dodecylamine, perfluoro‐1‐octanesulfonyl fluoride, and acryloyl chloride. Parameters affecting the intrinsic viscosity ([η]) and apparent viscosity (η) of FPAM, such as reaction temperature, AMPD concentration, AMPS concentration, monomer concentration, initiator concentration, and pH were examined. Apparent viscosity and interfacial tension (IFT) of FPAM solution were evaluated. Subsequently, temperature tolerance and shear tolerance were investigated by comparing with hydrolyzed polyacrylamide (HPAM), and results indicated that the FPAM displayed better performances than HPAM. FPAM can reduce the IFT between crude oil/water, and the IFT values are around at 2.91 and 3.9 mN m^?1 corresponding to FPAM and HPAM/FC‐118. The sandpack model oil displacement experiment showed that water flooding can further increase the oil recovery to 15.01% (FPAM), compared with 9.26% oil recovery for HPAM, and 10.99% oil recovery for HPAM/FC‐118. The glass micromodel techniques for studying enhanced oil recovery get a good result and provide a useful reference for understanding the displacement behaviors in polymer flood process. It could be concluded that the introduction of fluorinated groups in the polymer chain was helpful in enhancing the oil displacement efficiency. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44672.     

二元复合驱表面活性剂界面张力研究

研究了二元驱用植物改性羧酸盐表面活性剂SNHD与原油间的动态界面张力,并探讨了聚合物、矿化度、pH值以及时间对界面张力的影响。结果表明SNHD与原油的界面张力能达到超低值;聚合物对界面张力影响不大;矿化度对低活性剂浓度体系界面张力的影响较大,随矿化度增加,界面张力减小;体系的最佳pH值约为7。     

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.     

驱油阴/两性表面活性剂复配体系协同效应研究

针对某油藏A区块,利用阴离子/两性表面活性剂的协同作用,进而达到油水超低界面张力,且两性表面活性剂十二烷基甜菜碱在浓度为0.1%~0.5%的范围内,降低油水界面张力的效果达到10~(-2) mN/m数量级,在加入阴离子表面活性剂的条件下,复配体系可以使油水界面张力达到超低界面张力。通过探讨表面活性剂的总浓度以及复配比对油水界面张力的影响,最终得到阴离子/两性表面活性剂复配体系可在较高矿化度和较低的浓度(0.4%)范围内达到10~(-3) mN/m的超低界面张力,并在此基础上对两者的协同作用进行分析。     

Influence of polymer on dynamic interfacial tensions of EOR surfactant solutions

The effects of different types of polymers, partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM), on dynamic interfacial tensions (IFTs) of surfactant/model oil systems have been investigated by the spinning drop method in this article. Two anionic surfactants, 1,2‐dihexyl‐4‐propylbenzene sulfonate (366), 1,4‐dibutyl‐2‐nonylbenzene sulfonate (494) and an anionic–nonionic surfactant octyl‐[ω‐alkyloxy‐poly(oxyethylene)]yl‐benzene sulfonates (828) with high purity were selected as model surfactants. The influences of polymer concentration on IFT were expounded. It was found that the addition of polymer mostly results in increasing IFT because the interfacial molecular arrangement is modified owing to the interaction between polymer and surfactants. For HPAM, the polymer chains will enter the surfactant adsorption layer to form mixed‐adsorption layer. Therefore, HPAM shows strong effect on surfactant molecules with large size, such as 366. Conversely, surfactants can interact with the hydrophobic blocks of HMPAM and form mixed micelle‐like associations at interface. As a result, HMPAM shows more impact on IFT of 494 due to small steric hindrance for the formation of interfacial associations. This mechanism has been ensured by 828 molecules with two long alkyl chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40562.     

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     

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.     

Research on Oleic Acid Amide Betaine Used in Surfactant-Polymer Compound Flooding for Ordinary Heavy Oil

In view of the low recovery rate associated with water flooding, as well as the scaling problems caused by traditional alkali-surfactant-polymer flooding, the feasibility of using a betaine surfactant with high interfacial activity for chemical flooding of ordinary heavy oil was investigated. Aqueous solutions of oleic acid amide betaine (OAAB) with the mass concentration of 0.01% can reduce the oil–water interfacial tension to the ultralow level (10⁻³ mN m⁻¹), making it suitable for chemical flooding. To solve the problem of high adsorption onto sandstone, static adsorption tests and dynamic adsorption tests were carried out. The results show that the weakly alkaline lignin can significantly reduce the adsorption quantity of OAAB by more than 40%, based on which, a compound-flooding system of 0.1% partially hydrolyzed polyacrylamide (HPAM) + 0.1% OAAB +0.75% lignin was constructed. Compared with water flooding, the ultimate rate was enhanced by 20.4%, resulting in a final recovery rate of 53.9%. The study of oil displacement mechanism shows that the excellent ability to reduce the oil–water interfacial tension of OAAB can emulsify heavy oil to small droplets easily, exhibiting better capacity in oil displacement efficiency. The polymer can increase the viscosity of the aqueous phase, reduce the mobility ratio of water to oil, weaken the fingering effect, and improve the sweep efficiency. Lignin can not only reduce the adsorption quantity of betaine surfactant, but also promote the adsorption of OAAB onto the oil–water interface, leading to enhance the emulsification performance of OAAB and maintain the oil displacement efficiency effectively. Therefore, the surfactant-polymer flooding system based on the betaine surfactant can be developed into an economically and technically feasible flooding technology suitable for ordinary heavy oil reservoirs.     

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%.     

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.     

碱/烷基硫酸盐、烷基磺酸盐体系与原油间的动态界面张力的研究

合成了一系列高纯度的表面活性剂。在碱溶液中添加单一的表面活性剂 ,简化了驱油体系。考察了表面活性剂的结构、浓度与动态界面张力的关系。结果表明 ,只有当表面活性剂在两相的分配系数适当时 ,才具有较高的活性     

Surfactant-assisted aqueous extraction of palm-pressed mesocarp fiber residual oil with Tween 80 solution

The potential of Tween 80, a commercial food-grade non-ionic surfactant, was evaluated for the extraction of residual oil from palm-pressed mesocarp fibre (PPMF). Results show that the critical micelle concentration (CMC) was achieved at 0.05 wt% surfactant with an interfacial tension (IFT) of 0.51 mN/m. The extraction yield however depends not only on the IFT but also on the viscosity and the solid to liquid ratio of the extracting solution. The highest percentage of oil extraction (47.36%) was obtained at 1 wt% Tween 80 with 6% NaCl, temperature of 60°C and a solid–liquid ratio of 8 g PPMF: 200 g solution.     

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.     

Interfacial Tensions of Ethoxylated Fatty Acid Methyl Ester Solutions Against Crude Oil

The dynamic interfacial tension (IFT) of ethoxylated fatty acid methyl ester solutions against n‐alkanes, kerosene, and diluted heavy oil have been investigated by spinning drop interfacial tensiometry. The influences of ethylene oxide (EO) groups and alkyl chain length on IFT were investigated. The experiment results show that the water solubility decreases with an increase in alkyl chain length or a decrease in EO groups. The ability to lower the interfacial tension against hydrocarbons improves with both increasing alkyl chain length and EO group at the best hydrophilic‐lipophilic balance, which can be attributed to the enhancement of the interfacial hydrophobic interactions and the rearrangement of interfacial surfactant molecules. The mixed adsorption of surfactant molecules and surface‐active components may reduce IFT to a lower value. C₁₈=E₃ shows the best synergism with surface‐active components. However, the IFT values against pure crude oil are obviously higher than those against hydrocarbons, which may be caused by the nature of heavy oil.