三元复合驱碱/表面活性剂/聚合物模拟原油乳状液稳定动力学特性

基于两相分离的乳状液稳定模型,研究了三元复合驱模拟原油乳状液稳定动力学特性;通过液膜强度和油水界面张力探讨了碱/表面活性剂/聚合物对模拟原油乳状液稳定动力学特性的影响机理。 结果表明,乳状液稳定模型可以很好的评价乳状液的稳定性,并得到乳状液的稳定动力学特性;碱浓度小于900 mg/L有利于乳状液的稳定,碱浓度大于900 mg/L不利于乳状液的稳定;表面活性剂和聚合物浓度的增加使得形成的模拟原油乳状液更加稳定;模拟原油乳状液的稳定作用主要是通过碱、表面活性剂降低油水界面张力并增加油水界面膜强度,聚合物通过提高界面膜强度实现的,三者存在协同效应。     

Enhanced heavy oil recovery by organic alkali combinational flooding solutions

Although alkaline/surfactant/polymer (ASP) flooding is successfully applied in oil fields, some disadvantages such as scales, corrosion effects, and viscosity reductions of polymer solutions appear. Usage of organic alkalis can avoid or decrease these disadvantages. In this paper, the physicochemical properties, including interfacial tension (IFT), and viscosity, of organic alkali combinational flooding solutions and their effectiveness as enhanced oil recovery agents are investigated. Monoethanolamine (MEA) is the optimal one for decreasing the IFT among the three organic alkalis studied in this paper. Although MEA cannot decrease the IFT as low as NaOH does, it has good compatibility with both surfactant and the polymer hydrolyzed polyacrylamide (HPAM). MEA not only helps a surfactant solution or HPAM/surfactant mixture attain ultralow IFT values, but can also promote better viscosity stability for HPAM or HPAM/surfactant solutions compared to NaOH. Moreover, core flood experiments show that adding MEA can obtain additional tertiary oil recovery of 6%–10% original oil in place (OOIP) on the top of HPAM or HPAM/surfactant flooding, although MEA has a lower enhanced oil recovery than NaOH. The experimental results show that MEA is a good choice to replace NaOH in enhancing heavy oil recovery.     

Investigating the generation of ferrous sulfide nanoparticles in the produced fluid after acidizing oil wells and its influence on emulsifying stability between oil and water

Studies show that after acidizing operation of oil wells using the alkali/surfactant/polymer (ASP) flooding technology, the produced fluid is emulsified. Since the produced emulsion is stable, it affects the oil–water separation performance. In order to analyze the generation of stable emulsion in the produced fluid after acidizing an oil well, innovative separation experiments were carried out on real oil wells. During the experiments, solid particles in the middle layer of the emulsifying system in the produced fluid after acidizing ASP flooding were extracted and characterized. The generation of the stable emulsifying system in the produced fluid was studied through stability experiments and molecular dynamics simulations. The results showed that the synergistic effect of ferrous sulfide nanoparticles and surfactants was the fundamental reason for the strong emulsifying stability of the produced liquid after acidizing of the ternary composite system. The generation of ferrous sulfide solid particles mainly included two steps. First, sulfate reducing bacteria in injected water by ASP flooding reacted with sulfate in formation water to form hydrogen sulfide. Then, the hydrogen sulfide reacted with iron metal in oil wells and casing of wellbore to form ferrous sulfide particles. It was found that surfactants are adsorbed on the surface of ferrous sulfide nanoparticles. Subsequently, the control ability of surfactant on oil and water phases in the liquid film was enhanced. The performed analyses demonstrate that the adsorption of solid particles to the oil phase was enhanced, while the free motion of molecules in the oil phase at the liquid film position was weakened. The strength of the interfacial film between oil and water was further increased by the synergistic effect of ferrous sulfide nanoparticles and surfactant. The present study is expected to provide a guideline for a better understanding of the efficient treatment of produced fluids in ASP flooding.     

Characterization of suspended solids in produced water in Daqing oilfield

The concentration and size of suspended solids (SS) in the treated produced water beyond the criteria of injection water in Daqing oilfield have raised great concerns in recent years. The SS in produced water from water, polymer and alkali–surfactant–polymer (ASP) flooding were successfully separated and characterized using some analytical techniques in this study. X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and heating method reveal that some organic compounds besides crude oil were present in the SS samples, and polyacrylamide was found in the SS from polymer and ASP flooding. X-ray diffraction (XRD) shows some crystal inorganic substances such as SiO₂, Fe₂O₃, Fe₃O₄, and BaSO₄ in the SS samples, and XPS analysis indicated that several iron compounds with different valences were present in the three SS samples. The mean diameters of three SS samples were 22.89, 11.28 and 17.61 μm, respectively. Most importantly, the aggregates formed by the SS and oil droplets as well as the small SS adsorbed on the surface of oil droplets were observed using a microscope, indicating that the SS can be removed with crude oil, and crude oil also contributes to the determination of the SS values.     

油田采出液中微量羧酸盐表面活性剂分析方法研究

油田采出液中化学剂浓度的检测是三元复合驱动态评价的重要指标之一。本文针对现场提出的对微量羧酸盐表面活性剂的检测问题,建立了一种用紫外分光光度法测定微量羧酸盐表面活性剂分析的新方法。该法简便、准确快速,线性范围宽,回收率在94.4-103.1%之间,相对标准偏差为1.38%。并根据油田生产的实际情况,探论了碱、聚合物、原油等干扰因素对测定的影响,结果满意。     

碱对聚丙烯酰胺的分子形态及其流变性的影响

在碱、活性剂、聚合物三元(ASP)复合驱提高石油采收率的技术中,由于碱与聚合物分子的不相容性,严重地影响着驱油配方体系的研究及复合驱技术的推广.针对大庆油田的情况,利用HAAK流变仪,系统地研究了复合体系的流变性.结果表明,碱的加入明显地破坏了ASP复合体系的粘弹性.利用原子力显微镜,研究了碱对聚合物分子形态的影响.在无碱条件下,聚合物分子在液相充分舒展,而加入碱造成聚合物分子蜷缩,碱浓度越高,聚丙烯酰胺分子蜷缩成的线团越紧凑.在低浓度碱溶液中（质量分数0.3％）,聚合物分子也不能完全舒展,而是以多个分子侧向聚集状态存在.     

Study on Influencing Factors of Chemical Flooding for Heavy Oil

Alkali and alkali/surfactant displacing agents are designed for two kinds of heavy oil. Results of emulsifying capacity, dynamic interfacial tension (IFT) and water-wet core flooding tests show that, although alkaline/surfactant systems exhibit better capacity in emulsification and IFT reduction, oil recovery values of alkaline/surfactant flooding are lower than those of alkaline flooding. Glass-etched micromodel tests further demonstrate that, when alkaline solution penetrates into the oil phase, water streams break into ganglia coating oil film. Water ganglia may be entrapped by narrow throats, consequently presenting a water-oil alternating slug flow. Similar water ganglia also appears in alkaline/surfactant flooding, however, water channeling along the pore surface occurs subsequently, resulting in its relatively lower oil recovery.     

Effects of a Novel Organic Alkali on the Interfacial Tension and Emulsification Behaviors Between Crude Oil and Water

Experiments have been carried out to investigate the interfacial tension (IFT) and emulsification behaviors between Shengli crude oil and a novel organic alkali (OA). The dynamic IFT and minimum IFT are adopted to characterize the IFT behaviors; the microscopic method, Turbiscan stability index, separated water rate, and laser particle size analysis method are used to show the emulsification behaviors. The dynamic and minimum IFT both decrease continuously with the increase of OA concentration whether surfactant is added or not; because of the synergy of OA and surfactant, the minimum IFT will be reduced to the ultralow value. The synergy is also crucial for the crude oil emulsification. When OA and surfactant are used together, owing to the mosaic and cross-multiple adsorption of OA, surfactant and in situ soap at the interfacial film, the oil can be emulsified more easily, the quantity of emulsified droplets is higher, and the emulsion is more stable with OA concentration increases. The relationship of the minimum IFT and emulsification is investigated; it indicates that the emulsion stability improves, the degree of dispersed homogeneity of oil droplets increases, and the median diameter of emulsified oil droplets decreases with the decline of the minimum IFT.     

Relationship Between the Polymer Structures and Destabilization of Polymer‐Containing Water‐in‐Oil Emulsions

The viscous properties, scanning electronic microscopy (SEM), and water/oil interfacial tension (IFT) of partially hydrolyzed polyacryamide (HPAM) and hydrophobically associating hydrolyzed polyacryamides modified with N‐dodecylacrylamide were studied with the objective of investigating the influence on destabilization of emulsions. As expected, the copolymers exhibit significant viscosity enhancing capacity and three‐dimensional network structures due to intermolecular hydrophobic associations, and also present high interfacial activities as the IFT decrease with increasing polymer concentration. As a result, the existences of copolymers increased both the viscosity of emulsions and the intensity of interfacial film, in which case slow down the diffusion of demulsifier molecules and enhance the stability of emulsions, finally, the separation of water from oil becomes more difficult.     

Foam Flooding with Ultra-Low Interfacial Tension to Enhance Heavy Oil Recovery

Severe viscous fingering during water flooding of heavy oil leaves a large amount of oil untouched in the reservoir. Improving sweep efficiency is vital for increasing heavy oil recovery. Previous researches have proved that foam flooding can increase the sweep efficiency and oil recovery. The polymers could make the foam more stable and have better plugging capacity, but the interfacial tension (IFT) of oil and water increase which could decrease the displacement efficiency of the heavy oil. In view of the deficiency of conventional foam flooding, it is necessary to research the ultra-low interfacial tension foam which could improve macro-swept volume and micro-displacement efficiency in heavy oil reservoir. In this paper a novel foam agent is developed by the combination of surfactant and additives to lower the IFT of oil and water. The operating parameters including foam injections modes and gas liquid ratio were investigated by core flooding experiments. Field test performance shows that oil production per day increased from 85.6 to 125.7 t, water cut declined from 92.1 to 83.6% after 3 months injection. This study provides a novel method to improve heavy oil recovery with an ultra-low interfacial tension foam flooding system.     

Phase behavior and structure analysis of the middle mixed layer for ASP flooding system at low surfactant concentration

The phase behavior and interfacial tension of alkali/surfactant/polymer (ASP) flooding system and simulative crude oil were investigated, and the size distribution and structure analysis of the middle mixed layer (MML) were also studied by size analyzer and freeze-fracture TEM. It was found that there were some rules between the volume of MML and the concentration of each component, and the interfacial tension between MML and the oil phase or water phase could reach an ultra-low value. Especially, the freeze-fracture TEM micrographs of MML were firstly obtained, and the new viewpoint was put forward that there coexist the structures of micelle, microemulsions and emulsions in MML and the structure of microemulsion is dominant. This would make an important effect on the research of surfactant theory and ASP flooding mechanism.     

KINETICS OF COALESCENCE OF WATER DROPLETS IN WATER-IN-CRUDE OIL EMULSIONS

Water from water-in-crude oil emulsions is separated by chemical demul-sification. Coalescence rates of water droplets have been studied in the presence of a demulsifier. Droplet size measurement was carried out by photomicrography. Fastest coalescence rate was observed during first one minute. Binary coalescence time during this period was 5·4 seconds when 50 mg/1 of demulsifier was added and 4·2 seconds in the presence of 100 mg/1 of demulsifier.     

溶致液晶体系研究及其在三次采油中的应用

研究了石油磺酸盐/正戊醇/水的三元体系和石油磺酸盐/癸烷/正戊醇/水的拟三元体系相图中的液晶区域,揭示了不同组分对液晶区域大小的影响以及液晶的流变性和液晶的结构.在三次采油中,用六角状溶致液晶体系代替三元复合驱体系进行化学驱油,虽然驱油效率更高,但需要进一步降低液晶驱油体系的成本.     

Dynamic Interfacial Tension Behavior of Water/Oil Systems Containing In situ-Formed Surfactants

Time-dependent interfacial tension (IFT) has been investigated for an interfacially reactive immiscible system composed of model-acidified oil and alkaline water. The acidified oil was composed of either lauric acid or linoleic acid dissolved in n-dodecane. Drop volume tensiometry was employed to measure the interfacial tension between the two phases. In the case of lauric acid, the IFT value was found to decrease sharply with increasing alkali concentration, even at low drop formation times. In the case of linoleic acid, the IFT decrease with the drop formation time was more gradual, especially at low alkali concentration. The rate of formation of the interfacial area was also found to be dependent on alkali concentration.     

阴离子聚丙烯酰胺/三乙醇胺超分子体系的表征及性能

研究了水溶液和模拟矿化水溶液中带有负电荷的磺化聚丙烯酰胺(SPAM)与三乙醇胺(TEA)之间的相互作用及形成的超分子体系的结构特征,考察了超分子体系的形成对SPAM形貌、流体力学直径、zeta电位、黏度及流变学性质的影响.研究结果表明,超分子体系的形成有利于提高磺化聚丙烯酰胺的黏度、抗剪切性、剪切回复性及抗温耐盐性.     

What is the Criterion for Selecting Alkaline/Surfactaint/Polymer Flooding Formulation: Phase Behavior or Interfacial Tension

An experimental study on determination of alkaline, surfactant, polymer (ASP) flooding systems using natural mixed carboxylate was conducted to examine the decisive factor for ASP flooding, phase behavior or interfacial tension. The volume and color of middle phase liquid were observed, the transient interfacial tension at different salt and alkaline concentrations were measured and, finally, coreflood test in laboratory were made. The results showed the flooding system with larger volume and brown color of middle phase emulsion sometimes not to obtain better oil recovery efficiency. The primary and more important phenomenon affecting the oil recovery is a lower or ultralow minimum interfacial tension value at the crude oil/soluble phase interface.     

Interfacial activity of a novel family of polymeric surfactants

A novel series of polymeric surfactants based on carboxy methyl cellulose and alkyl poly(etheroxy) acrylate were synthesized by ultrasonic irradiation. These polymeric surfactants have exhibit excellent surface activity due to their unique structure. The influences of salt, alcohol and alkali on the interfacial activity of these polymeric surfactants were studied by interfacial tensiometery, dynamic laser scattering (DLS), UV spectroscope and environmental scanning electrical microscope (ESEM). The surface tension and interfacial tension (IFT) properties change little with NaCl added. The formed micelles shrink, their size becomes smaller. Alcohols cause the IFT to decrease a little because a small amount of free chains present in solution. Under the influence of added alkali, the IFT of the polymeric surfactants, in aqueous solution, decreases so much that sometimes it is less than 10⁻² mN/m. Using data from the equivalent alkane scan, one cannot draw the conclusion that the action of alkali with the acidic components in crude oil leads to the ultra-low IFT. The analyses by UV, DLS and ESEM show that the micelles formed by polymeric surfactants could be disaggregated or destroyed sharply by the action of alkali. So the size of micelles decreases greatly and the number of free chains increases. That more polymeric surfactants molecules move to the interface of oil/water and rearrange at the interface of oil/water is believed to be the main reason of the ultra-low IFT (10⁻³ mN/m) that is obtained.     

CMC系列高分子表面活性剂与原油超低界面张力形成机理的研究

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素系列高分子表面活性剂与大庆原油形成超低界面张力的机理.结果表明,CMC系列高分子表面活性剂具有与低分子量表面活性剂相比拟的表/界面活性,其水溶液的表面张力可达2835mN/m,界面张力达到10^-110mN/m.碱的加入可显著降低高分子表面活性剂与原油的界面张力,在适当条件下界面张力达到超低值(10^-3mN/m),可望作为三次采油的驱油剂.等效烷烃模型研究表明,用碱与原油酸性组分的作用来解释碱能使界面张力下降至超低值的传统观点是不完善的,加入碱能使高分子表面活性剂胶束解缔,胶束数量增多,胶束粒径减小,单分子自由链增加,有利于高分子表面活性剂向界面迁移和排布,这是高分子表面活性剂和碱复配体系与原油界面张力下降至超低值的主要原因.     

Synthesis of a new sulfobetaine surfactant with double long alkyl chains and its performances in surfactant-polymer flooding

A new zwitterionic surfactant with double long alkyl chains, 3-((3-((1,3-bis (decyloxyl) propane-2-yl) oxy) -2-hydroxypropyl) dimethylamonio) -2-hydroxypropane-1-sulfonate (diC₁₀GE-HSB), was synthesized, and its performances in Surfactant-Polymer (SP) flooding were studied. As a hydrophobic surfactant diC₁₀GE-HSB solely cannot reduce Daqing crude oil/connate water IFT to ultralow, but ultralow IFT can be achieved by using binary mixtures of diC₁₀GE-HSB with various conventional hydrophilic surfactants such as α–olefin sulfonates, dodecyl polyoxyethylene (10) ether, and cetyl dimethyl hydroxypropyl sulfobetaine, over a wide total concentration range (0.625?～?10?mM) at reservoir temperature. This new sulfobetaine surfactant is therefore a good candidate for SP flooding free of alkali.     

Dipolar anions are not preferentially attracted to the oil/water interface

Homogenization of hexadecane in water at pH 9 gives the same surface charge density in the presence of 0.2 mM thiocyanate or acetate anions as in the presence of chloride, indicating that these dipolar anions are not preferentially adsorbed at the oil/water interface. The decrease in the zeta potential of the emulsion droplets as the sodium salts of iodate, thiocyanate, or acetate are added from 0.1 to 10 mM is the same as that when sodium chloride is added, leading to the same conclusion. Increasing the sodium hydroxide concentration from pH 9 to 11.5 has a different effect on the zeta potential, consistent with the specific adsorption of hydroxide ion at the oil/water interface.