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.     

Experimental Investigation of Noble Viscoelastic Surfactant and Chelating Agent for Heavy Oil Enhanced Oil Recovery in High-Pressure–High-Temperature Carbonate Reservoirs

The success of chemical enhanced oil recovery (cEOR) is significantly dependent on the type of reservoir and its pressure and temperature conditions. The recovery of heavy oil from carbonate reservoir using cEOR method is still challenging because of its highly complex internal structures and high pressure–high temperature (HPHT) conditions. This research work is the first account of the use of AGA-97 (viscoelastic surfactant [VES)) along with a chelating agent diethylene triamine penta acetic acid (DTPA) for their application in cEOR method in heavy-oil-carbonate reservoirs. Several core flooding experiments were carried out to ascertain the effectiveness of the VES AGA-97 and chelating agent for cEOR method. The effect of VES on viscosity and interfacial tension was also studied with varying concentration, temperature, and time. The thermal stability of VES was analyzed with the help of thermogravimetric analysis, nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy. VES AGA-97 was found to have high thermal stability in short-term aging. The static adsorption and dynamic adsorption of VES AGA-97 was studied with the help of total organic carbon analysis. After all the analysis, it was found that VES AGA-97 and DTPA can be effectively used for cEOR method in carbonate reservoir at HPHT conditions, and the total additional oil recovery of 5.82–9.64% may be achieved.     

注气过程中沥青质沉淀对孔隙型碳酸岩油藏储层伤害的实验研究

中东地区大部分油藏属于孔隙型碳酸岩油藏,开发初期采用衰竭开采,中后期二次采油基本采用注气方式。而无论是衰竭开采还是注气提高采收率,沥青在地层和井筒沉淀都是一个普遍现象。它是制约原油生产的一个重要因素,本次重点研究了实验模拟条件下注气过程中沥青沉淀对储层的伤害程度。这对于中后期注气开发过程中控制沥青沉淀,提高原油采收率有重要的意义。实验表明:沥青沉淀会对储层的孔隙度和渗透率造成伤害,不同的注入速度对储层的伤害程度不同,注入速度较高时,沥青沉淀对储层的伤害更严重;气驱后注入气体突破对储层的伤害进一步加剧。因此在对油藏特别是孔隙型低渗透碳酸岩油藏实施注气时,尽量延长气体突破的时间,同时针对沥青沉淀需采取一定的预防措施。     

Preparation and properties of novel pH‐sensitive core−shell microspheres for enhanced oil recovery

A novel pH‐sensitive core?shell microsphere was synthesized by growing sodium acrylate as a shell on crosslinked polyacrylamide particles as the core by surface‐initiated atom transfer radical polymerization. The structures and characteristics of the microspheres were confirmed by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, SEM, transmission electron microscopy and AFM. The viscosity and size of the microspheres in response to changes in pH value were also investigated. As a kind of potential profile control and flooding agent, the performances of permeability reduction and enhanced oil recovery were studied in designed experiments. © 2017 Society of Chemical Industry     

油酸钠蠕虫状胶束的性质及驱油效率研究

分别通过稳态、动态流变的方法和冷冻蚀刻透射电镜、室内模拟驱油实验和平板夹砂微观模型驱油实验,研究了由碳酸钠诱导形成的油酸钠蠕虫状胶束的流变学性质及形貌和蠕虫状胶束驱油配方的驱油效果及驱油微观机理。结果表明,在油酸钠(NaOA)溶液中,加入一定量的Na2CO3能够形成蠕虫状胶束;孤岛东区稠油注聚驱后,蠕虫状胶束驱油配方(w/%,1.83 NaOA 4.24 Na2CO3)的室内模拟驱油可提高采收率25%原始石油地质储量(OO IP);平板夹砂微观驱油模型显示蠕虫状胶束驱油体系进入模型中,能够使注聚后束缚残余油重新启动、变形,渐渐形成油墙向出口处运移,蠕虫状胶束驱油体系能够有效扩大波及体积,提高洗油效率,从而提高驱油效率。     

Effect of Nanoparticles on Viscosity and Interfacial Tension of Aqueous Surfactant Solutions at High Salinity and High Temperature

Surfactant flooding has widely been used as one of the chemically enhanced oil recovery (EOR) techniques. Surfactants majorly influence the interfacial tension, γ, between oil and brine phase and control capillary number and relative permeability behavior and, thus, influence ultimate recovery. Additives, such as nanoparticles, are known to affect surfactant properties and are regarded as promising EOR agents. However, their detailed interactions with surfactants are not well understood. Thus, in this work, we examined the influence of silica nanoparticles on the ability of surfactants to lower γ and to increase viscosity at various temperatures and salinities. Results show that the presence of nanoparticles decreased γ between n-decane and various surfactant formulations by up to 20%. It was found that γ of nanoparticles–surfactant solutions passed through a minimum at 35 °C when salt was added. Furthermore, the viscosity of cationic surfactant solutions increased at specific salt (1.5 wt.%) and nanoparticle (0.05 wt.%) concentrations. Results illustrate that selected nanoparticles–surfactant formulations appear very promising for EOR as they can lower brine/n-decane interfacial tension and act as viscosity modifiers of the injected fluids.     

黏弹性表面活性剂及其在油田中的应用

介绍了黏弹性表面活性剂溶液的性质，确定黏弹性表面活性剂性质的测试方法和实验手段，以及其内部微观结构和流变特性等方面的研究成果。当黏弹性表面活性剂溶液浓度增加到某一临界浓度时，球形胶束开始向蠕虫状胶束转变，溶液黏度突然增大，随着浓度的进一步增大，蠕虫状胶束快速生长、增长并形成线型柔性棒状胶束，柔性棒状胶束相互缠绕、粘附甚至融合，形成某种超分子三维网状结构，溶液黏度急剧增加，并表现出较强的黏弹性。概述了黏弹性表面活性剂在油田中的应用，特别是在压裂液、酸液、钻井液及提高采收率等方面的应用，指出了黏弹性表面活性剂广泛运用的前景和尚未解决的问题。     

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.     

Study on rheology and thermal stability of mixed (nonionic–anionic) surfactant based fracturing fluids

Mixed surfactant systems have gained significant importance in the development of fracturing fluid due to polymorphism of self‐assembly structures that have combined properties of the surfactants in the mixture. In this article, a comparative study on the phase behavior and viscoelastic properties of mixed surfactant based fluids, prepared from Tween 80+NaOA/2‐ethyl hexanol/clove oil/water and Tween 20+NaOA/2‐ethyl hexanol/clove oil/water quaternary system is investigated in details. The viscoelastic surfactant (VES) based fluids prepared from the former system offered superior rheological properties than the latter system. The addition of 0.1% NaOH and 500 ppm ZnO nano‐particles in the VES fluids presented enhanced viscoelastic properties as concluded by static and dynamic rheological tests. Miscibility test indicated the miscibility of the VES fluids with water, unlike in the presence of diesel oil and satisfactory proppant suspension capabilities were exhibited by the developed fluids. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2177–2187, 2016     

复配表面活性剂减缓水锁效应的实验研究

制取了非离子氟碳表面活性剂FPEG400和FPEG600,并与甲醇进行复配得到了复配表面活性剂。室内水锁实验研究结果表明：水驱过程中加入该复配表面活性剂后。岩心的渗透率损害程度得到较大的降低。油相渗透率上升,提高了采收率。     

Z2断块储层特征研究

应用恒速压汞以及核磁共振技术研究了Z2断块低渗透储层的微观孔隙结构以及可动流体特征,并分别建立了主流喉道半径、可动流体百分数与储层渗透率的关系;最终以主流喉道半径、可动流体百分数、粘土矿物含量、原油粘度为指标,依据储层评价标准,对Z2断块的三个层系进行了储层分类1,分类结果表明,三个层系均为Ⅰ-Ⅱ类储层,开发较为容易。研究成果为分析评价同类储层并指导增储上产提供了可靠的科学依据。     

Rapid and Simple Identification and Quantification of Components in Detergent Formulations by Nuclear Magnetic Resonance Spectroscopy

A rapid, inexpensive, and simple high-resolution NMR spectroscopic method is outlined for determining the content of surfactants and other low-molecular-weight organic compounds in detergent formulations. With simple sample preparation, quantitative results can be obtained from an internal standard and/or the method can be used as a fingerprint analysis of the surfactant composition. The NMR sample is prepared by suspending the detergent sample in deuterated acetic acid and thus dissolving surfactants and other organic compounds. Any content of carbonate will be liberated as CO₂, whereas other inorganic materials are removed by centrifugation. From one-dimensional ¹H and two-dimensional HSQC NMR spectra, the surfactant components and low-molecular-weight organic compounds can be identified from reference spectra. Intensities of signature signals in the one-dimensional ¹H NMR spectrum are used for quantification by comparing with an internal standard. Furthermore, it is demonstrated how ³¹P NMR can be used to identify and quantify phosphonate-type chelators.     

A method to calculate the multiphase flow properties of heterogeneous porous media by using network simulations

A method is suggested to compute the capillary pressure and relative permeability curves of heterogeneous porous media. The broad pore radius distribution (PRD) and throat radius distribution (TRD) are decomposed into relatively narrow component distribution functions which are used for the computer‐aided construction of pore‐and‐throat networks. The quasi‐static motion of menisci in pores and throats is tracked by accounting for capillary forces. The presence of fractal roughness along pore walls ensures the coexistence of both phases in pores. The calculation of the hydraulic conductance of each phase is based on the concept of constricted unit cell. Simulations in component pore networks constructed from narrow PRD and TRD produce a set of capillary pressure and relative permeability functions, the arithmetic averaging of which yields the corresponding functions for a heterogeneous synthetic pore network. This information is used by a dynamic simulator of drainage in permeability networks to predict experimental results of soil columns. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

弱碱三元体系对孔隙结构影响研究

ASP三元复合驱能扩大波及体积并且提高驱油效率,同时能极大的降低表面活性剂用量,使具有极其良好的技术经济可行性。通过常规压汞实验及扫描电镜实验分析研究了岩心在弱碱三元驱后的孔隙结构特征,对比分析了弱碱三元体系渗流前后岩心的孔隙结构特征变化。对其结果分析可知,由于弱碱三元体系对储层岩石有一定的溶蚀作用,当弱碱三元体系进入小孔道时,对小孔道的溶蚀导致小孔道半径变大,减少小孔道的数量,增多大孔道的数量,从而略微增大整体岩心的渗透率。弱碱三元复合驱前岩石致密,孔隙较小且比较均匀。弱碱三元复合驱后,出现斑驳状凸起,孔隙发育比较明显,岩石上有可动碎屑附着。碱的浓度越高,三元体系对岩心的溶蚀作用强烈,对岩心伤害程度更大。     

Performance of PAM/PEI gel system for water shut‐off in high temperature reservoirs: Laboratory study

A polymer gel is one of the common remediate methods to either reduce or totally block excessive water production in oilfields. Some systems demonstrated an excellent performance in treating the problem like polyacrylamide tert‐butyl acrylate (PAtBA)/polyethylenimine (PEI). In this study, polyacrylamide (PAM) was introduced as a cheap alternative to PAtBA that can tolerate high salinity reservoirs. The thermal stability of the PAM/PEI polymeric gel in saline water was examined at 150°C (302F). Samples prepared in sea water showed better stability compared with distilled and field water. Dynamic rheology and core‐flooding experiments were used to evaluate the PAM / PEI gel system at high temperatures. NaCl and NH₄Cl were evaluated as a possible retarders for delaying the gelation time in order to achieve a successful placement. NH₄Cl was found to be more effective retarder. Core‐flooding tests were conducted in sandstone and carbonate cores. The subject polymer gel was injected at rates typical of those in field applications. The injectivity of PAM/PEI was tested in Berea sandstone cores with initial permeability of ～45 mD. The post‐treatment of the system showed a permeability reduction of ～94% for a period of two weeks. The injectivity in low permeability carbonate cores required more retardation compared with the injectivity in sandstone cores. The gel reduced the permeability to brine in Indiana limestone core by 99.8% for more than 5 months. Rheology of cured gel samples indicated that the gel strength needs about one day of curing in the core for the strength to stabilize. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41869.     

低渗透储层的微观孔隙结构特征研究

本文以鄂尔多斯盆地低渗透储层为例,在岩芯观测、岩石薄片、铸体薄片、扫描电镜以及压汞资料分析的基础上,分析了该地区低孔低渗砂岩的岩石学特征、储层物性及微观孔隙结构特征;分析了储层有效喉道半径、有效喉道体积、有效孔隙半径、有效孔隙体积及孔喉比等特征参数与孔隙度、渗透率之间具有较好的相关性。     

Application of pH-Responsive Viscoelastic Surfactant as Recyclable Fluid at High Temperature

A pH-responsive amphiphilic surfactant stearic amide 3-(N,N-dimethylamino)propylamide (SAA) was synthesized and served as a thickener in aqueous solution to construct a switchable viscoelastic surfactant fluid (VES fluid). The structure of SAA was studied by ¹H NMR, and the viscoelastic behavior of VES fluid was studied in detail by rheological measurements. The viscosity of this VES fluid can be switched reversibly from low to high immediately by adjusting system pH value. Even at high shear rate (170 s⁻¹) and high temperature (90 °C), excellent viscoelastic behavior of this VES fluid can be observed, which is a key performance for fracturing applications. Meanwhile, the recycled VES fluid can still maintain good pH-responsive behavior even after more than three cycles. These unique performances of this VES fluid not only enhanced our understanding of the transformation of wormlike micelles at high temperature, but also enriched a large potential of VES fracturing fluid in the development of oil and gas reservoirs.     

Understanding the role of isocyanate dilution toward spraying of polyurea

An experimental study into the consequences of diluting isocyanate toward processing of polyurea has been reported. The effect of introducing increasing amount of propylene carbonate into a representative isocyanate precursor has been established. Viscosity‐blending index based equations were found to be more reliable toward prediction of isocyanate precursor‐propylene carbonate blend viscosity. Spraying of undiluted isocyanate precursor with amine formulations led to formation of “noodle‐like” fibrous product, irrespective of the type of chain extender being used. Diluting isocyanate with propylene carbonate (10% v/v), lowered the viscosity of the precursor from 85 to 48 mPa s (at 70 °C), and the resulting formulations could be effectively sprayed to form polyurea films with excellent mechanical properties. Dilution with propylene carbonate also increased the “tack free” time appreciably from ～1 to ～4 s, which directly reflects on the improved processability. Rheological studies were performed to quantify the activation energy associated with the isocyanate‐amine reaction for polyurea preparation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45869.     

阴离子型VES压裂液在裂缝性油藏中的研究应用

裂缝性油藏中出现的天然裂缝会在水力压裂过程中发生剪切或者破坏等一系列现象,这导致了压裂液的滤失情况十分严重,进一步造成砂堵或者加砂困难等问题。针对裂缝性油藏中压裂液滤失严重的问题,通过研究阴离子型VES压裂液的性能来降低压裂液的滤失量。测试了VES压裂液的流变性能、耐温性能、粘弹性能、悬砂性能及破胶性能。研究表明,VES压裂液的耐剪切性很好,可以维持长时间的工作要求,在低剪切力下可以维持粘度的不变,在提高剪切速率时粘度会开始下降,在剪切速率得到回降后粘度又可以快速恢复;VES压裂液在60℃的地层中利用率最高,此温度下的粘度最大,弹性也最大,不可用于高于80℃的地层;VES压裂液支撑剂沉降速度很低悬砂性能很好,破胶很快且很彻底;这些优越的性能可以大量减少裂缝性油藏在水力压裂过程中压裂液的滤失量。