Detection and Reuse of the Produced Chemicals in Chemical Enhanced Oil Recovery Operations

The alkaline-surfactant-polymer (ASP) floods have been increasingly applied in the oil fields because of their high ultimate oil recovery. However, a major technical challenge is how to reduce the amount and the cost of chemicals used so that ASP floods can become cost-effective as well. On the other hand, field applications show that the chemical concentrations remain relatively high in the produced liquids of ASP floods. Therefore, successful detection and reuse of these produced chemicals can substantially reduce their capital cost and environmental impact. In this article, several experimental methods are developed to detect each chemical and quantify its concentration in the produced liquids. Also re-injection of the produced chemicals is conducted to further enhance oil recovery. First, the respective interactions of alkali, surfactant, and polymer with the oil-brine-sand system are studied. Second, the interfacial tension (IFT) is measured as a function of alkaline concentration by using the axisymmetric drop shape analysis technique for the pendant drop case. In addition, the synergistic effects of alkali and surfactant on reducing the IFT are studied. Third, coreflood tests are performed for alkaline, surfactant, alkaline-surfactant, polymer, and ASP floods to determine their respective tertiary oil recovery. Hence, how each chemical contributes to enhanced oil recovery is better understood. Fourth, the produced chemical concentrations are measured and compared with their injected concentrations to determine the potential of reusing these chemicals in practice. Finally, the follow-up coreflood tests are conducted by re-injecting the produced liquids into a new sand pack or Berea core. The re-injection coreflood test results show that the produced chemicals can be reused to effectively enhance oil recovery.     

华北油田京11断块三元复合驱配方研究

针对华北油田京11断块油藏原油黏度低、酸值低、水驱采收宰高和储集层黏土含量高等特点，优选得到适合于该油藏的最佳低浓度弱碱三元复合体系：2SY重烷基苯磺酸盐表面活性剂(0．15%)／Na2C03(0．5%)／SY(1．5g／L)。采用实验方法，系统研究京11断块环境因素对该三元复合体系的界面张力性质、流交性以及表面活性剂和碱剂吸附损耗的影响，结果表明：该体系对矿化度、多价金属离子浓度变化以及稀释效应等环境因素影响的耐受性较强。物理模型驱油效率试验结果表明：在水驱至含水98%后，相继注入0．3倍孔隙体积最佳三元复合体系主段塞和0．2倍孔隙体积1．2g／L聚合物溶液保护段塞，可提高采收率21%以上。图3表6参7     

三元复合体系相行为特征及其对驱油效果影响

针对大庆油田改善三元复合驱的实际需求,通过测试三元复合体系在驱油实验前后粘度和界面张力变化,讨论了表面活性剂、碱和盐等化学剂浓度变化对三元复合体系相行为特征和采收率的影响。实验结果表明,表面活性剂除了能降低界面张力外,还有利于增加体系的粘度,碱能促进原油的乳化,盐对复合体系相行为变化比较敏感。研究结果还发现,碱和盐在复合驱驱油机理上有相似之处,盐可以部分替代碱,这不仅能够减小碱对地层伤害、优化复合体系配方,而且可以取得较好的经济效益。     

The Effect of Alkali and Surfactant on Polymer Molecular Structure

Abstract

With the technical development of enhanced oil recovery (EOR), the alkali/surfactant/polymer (ASP) compound flooding technique has been the necessary choice in Daqing oilfield. Compared to average polymer flooding, ASP compound solution decreases the interfacial tension (IFT) between water and crude oil; however, the viscosity and viscoelasticity of ASP solution were performed by surfactant and alkali, both of which could affect the polymer moleculal structure and the oil recovery of ASP flooding. Considering practical requirements in oilfield development, much effort has been focused on the effect of alkali and surfactants on polymer solution by laboratory experiment and theoretical analysis. The results indicate that alkali and surfactants cause the interfacial tension decrease; at the same time, the molecular structure of the polymer is changed and the viscosity and viscoelasticity of polymer solutions are decreased. In addition, alkali neutralizes with negative ion on polymer molecular and causes the polymer molecular chains to curl up, forming a “band” molecular structure. Those actions could make viscoelastic behavior and rheological property of ASP solution weak.     

碱对复合驱油体系与原油乳化作用的影响

碱、表面活性剂和聚合物组成的ASP复合体系中,加入的碱一方面能够使ASP复合体系与低酸值原油之间的界面张力降至很低水平,同时对乳化也起到重要作用,而碱的类型和加量直接影响该体系和原油形成界面张力的数量级及油水的乳化程度,因此系统分析了碱对乳状液形成及其稳定性的影响规律,有助于探讨碱在三元复合体系乳化过程中的作用机理。采用自行建立的乳化程度评价指标,对比了不同碱加量下的乳化程度,并采用析水率曲线评价了乳状液的稳定性。结果表明,随着碱含量的增加乳化程度增强,说明低界面张力有利于乳状液的形成;同时NaOH的质量分数在0.1%～0.3%时,复合体系与大庆油田原油形成的乳状液最稳定。      

用正交试验设计方法寻找三元复合驱油体系配方的研究

以胜利油田孤岛试验区原油为油相,根据原油与驱油体系之间的相态扫描和界面张力变化情况,应用正交试验设计方法,筛选出最佳的碱／表面活性剂／聚合物三元复合驱油体系配方,能提主采取率２６．２％（ＯＯＩＰ）。     

三元复合驱对储层伤害及其作用机理研究

三元复合驱能够大幅度提高原油采收率,但它所引起的结垢问题一直困扰着该技术的大规模推广应用。本文以大庆喇嘛甸油田储层岩石和三元复合体系为实验对象,开展了碱驱后岩石结构的可视化研究以及含碱驱油剂流动特性研究。实验结果表明,碱对储层岩心中黏土矿物溶蚀作用比较明显,对石英和长石等骨架成分的溶蚀作用较小;采出液中钙镁离子浓度较低,硅离子浓度却较高,前者成垢作用难以对储层渗透率造成显著影响,后者易在迁移过程中发生沉积,在地层和生产系统中形成大量硅垢。进一步分析表明,随碱浓度增加,三元复合体系对地层伤害程度加剧。表面活性剂和聚合物都可以减弱碱的溶蚀作用,但前者比后者减缓溶蚀作用的能力弱。     

不同驱油体系在贝雷岩心中的驱替特征

为了保持室内岩心驱油实验中孔隙结构对驱替剂驱油效果的影响与实际砂岩油层孔隙结构的影响一致,使用气测渗透率300×10-3μm2的贝雷、人造、天然均质岩心进行常规压汞实验和驱油实验.研究了不同类型岩心孔隙结构差异及其对驱油效果的影响,分析了不同驱油体系在贝雷岩心中的采收率及注入压力变化.实验结果表明:贝雷岩心与天然岩心在孔喉结构上有一定的相似性,能够充分体现各种体系的驱油效果;在贝雷岩心中,保持体系黏度、表面活性剂质量浓度相同条件下,化学驱采收率由高到低顺序为弱碱三元体系、强碱三元体系、聚合物—甜菜碱表活剂体系、聚合物体系,三元复合驱后续水驱阶段采出的油量对化学驱采收率的贡献较大,驱油过程中体系是否发生乳化对驱油体系的驱油效果存在明显影响;聚合物溶液和三元体系驱替过程中的压力存在明显的不同,聚驱过程中的主要特点是注化学剂过程结束后压力快速下降,复合驱压力变化曲线主要特点是注化学剂结束后水驱阶段压力先上升后下降,乳化—捕集机理是造成注入压力曲线形态差异的主要原因.     

Performance comparison of novel chemical agents in improving oil recovery from tight sands through spontaneous imbibition

Tight sands are abundant in nanopores leading to a high capillary pressure and normally a low fluid injectivity.As such,spontaneous imbibition might be an effective mechanism for improving oil recovery from tight sands after fracturing.The chemical agents added to the injected water can alter the interfacial properties,which could help further enhance the oil recovery by spontaneous imbibition.This study explores the possibility of using novel chemicals to enhance oil recovery from tight sands via spontaneous imbibition.We experimentally examine the effects of more than ten different chemical agents on spontaneous imbibition,including a cationic surfactant(C12 TAB),two anionic surfactants(0242 and 0342),an ionic liquid(BMMIM BF4),a high pH solution(NaBO_2),and a series of house-made deep eutectic solvents(DES3-7,9,1 1,and 14).The interfacial tensions(IFT) between oil phase and some chemical solutions are also determined.Experimental results indicate that both the ionic liquid and cationic surfactant used in this study are detrimental to spontaneous imbibition and decrease the oil recovery from tight sands,even though cationic surfactant significantly decreases the oil-water IFT while ionic liquid does not.The high pH NaBO_2 solution does not demonstrate significant effect on oil recovery improvement and IFT reduction.The anionic surfactants(O242 and O342) are effective in enhancing oil recovery from tight sands through oil-water IFT reduction and emulsification effects.The DESs drive the rock surface to be more water-wet,and a specific formulation(DES9) leads to much improvement on oil recovery under counter-current imbibition condition.This preliminary study would provide some knowledge about how to optimize the selection of chemicals for improving oil recovery from tight reservoirs.     

用于三次采油的新型弱碱表面活性剂

以α-烯烃为初始原料,经过烷基化及磺化、中和,研制出了组分相对单一、结构合理的新型弱碱烷基苯磺酸盐表面活性剂.室内评价结果表明,这种表面活性剂具有良好的界面活性,配制的复合体系在较宽的表面活性剂浓度和碱浓度范围可与原油形成10^-3mN/m数量级的超低界面张力.同时,该表面活性剂对大庆油田不同区块、不同油层的油水条件有很强的适应性.另外,由于表面活性剂组成较为单一,可大大降低表面活性剂在地层中因吸附滞留而产生的色谱分离效应.室内天然岩心驱油实验表明,三元复合体系平均驱油效率可比水驱提高约20%.小井距三元复合驱矿场试验结果表明,三元复合驱比水驱提高采收率24.66%.这种表面活性剂为三元复合驱技术在大庆油田的工业化推广,特别是在二类油层的应用奠定了基础.     

Wettability Modification of Fractured Carbonates Using Sodium Metaborate Part II: History Match Results and Sensitivity Simulations

Abstract

Chemical-based wettability modification has become important for the worldwide abundance of fractured carbonates with the potential to enhance water imbibition to expel more oil from a matrix to the fractures. A systematic experimental and modeling approach on the combined benefit of wettability alteration for enhanced water imbibition and interfacial tension reduction is presented. Brine, alkali, and alkali–surfactant solutions are injected sequentially to improve oil recovery from a fractured mixed-wet carbonate core. The experiment was successfully modeled with a 3D chemical flooding reservoir simulator with wettability alteration capability. Part I discussed the laboratory results and presented the modeling approach and the waterflood history match results. The history match procedure and results for wettability modification using an alkali agent and interfacial tension (IFT) reduction with surfactant are discussed in this article. Sensitivity simulations to some key parameters are also presented.     

化学复合驱技术研究与应用现状及发展趋势

近年来化学复合驱技术应用基础研究及现场试验得到了长足发展。国内采用低浓度复合驱体系,通过碱、表面活性剂的协同作用,降低油水界面张力达到超低数量级,同时采用抗盐聚合物使污水配制驱替液黏度达到要求,三元复合驱或二元复合驱具有提高驱油效率和扩大波及体积双重作用。大庆油田三元复合驱先导性试验和工业化试验提高采收率幅度达到18.6%～26.5%,复合驱进入工业化推广应用阶段,在复合驱试验过程中逐步形成了系列配套技术。复合驱存在的主要问题为强碱引起的检泵周期较短和采出液处理难度大、成本高。国外复合驱技术早期主要采用表面活性剂胶束-聚合物驱,由于成本高未能推广应用,近年来随着油价上涨,开始研究低浓度复合驱体系。国外采用化学驱的油藏大部分为高温高盐油藏,瓶颈技术为耐温抗盐驱油剂的研制。     

The Demulsification of Crude Emulsion of ASP Flooding by an Organic Silicone Demulsifier

Abstract

In order to enhance crude oil recovery, the dosages of alkali, surfactant, and polymer in the tertiary flooding are becoming increasingly higher, which makes the emulsion more difficult to demulsify. In this article the application of new organic silicone demulsifiers for the demulsification of produced crude emulsion of alkali-surfactant-polymer (ASP) flooding with higher concentrations of alkali, surfactant, and polymer was investigated. The result indicated that organic silicone demulsifiers whose hydrophile–lipophile balance (HLB) number ranged from 10 to 15 had a satisfactory effect on demulsification. The dewatering efficiency can be improved evidently by adding a demulsifier mixed with DC2 and JG31 whose volume ratio was 4:1. The dewatering efficiency for produced crude emulsion from ASP flooding could exceed 80% at 60°C in which the concentrations of alkali, polymer, and surfactant ranged from 1,200 to 9,000 mg/L, 400 to 1,000 mg/L, and 200 to 800 mg/L, respectively. The simulative industrialized experiment of the ASP flooding produced emulsion was made, the dewatering efficiency was 99.6%, and the oil content of the produced water was less than 100 mg/L.     

Investigating the role of polymer type and dead end pores’ distribution on oil recovery efficiency during ASP flooding

Although alkaline-surfactant-polymer flooding is proved to be efficient for oil recovery from petroleum reservoirs, effects of existence of dead end pores on this process need more discussions. In this work, several ASP flooding tests constituted from 4 polymers, 1 surfactant and 1 alkaline were performed on micromodels designed in four various dead end pore distributions initially saturated with crude oil. The results showed that although using ASP solution constituted from hydrolyzed polymers at high molecular weights significantly increases oil recovery factor due to increasing apparent viscosity of the solution, using sulfonated polymers in ASP solution increases oil recovery much more because of their capability to increase viscosity even in saline solutions. In addition, it was concluded that the number of dead end pores as well as their distribution with respect to the flow direction are two main characteristics that identify the efficiency of brine and ASP floods in dead end porous media. Moreover, although in ASP flooding, since the viscosity is higher and the front is flatter, the role of the number of dead ends on the recovery efficiency is more identifiable than the role of dead ends’ distribution, in waterflooding, since the mobility ratio is not low enough, the role of dead end direction with respect to the flow direction plays a more significant role in recovery process. So, considering the efficient direction of injection is too important during waterflooding and chemical EOR especially in reservoirs that have a remarkable percentage of dead end pores in their geological structure.     

Evaluation of Interfacial Tension Between Zahra Oil and ASP Solution

Alkaline-surfactant-polymer (ASP) flooding has been proved to be an effective enhanced oil recovery (EOR) method. Reduction of interfacial tension (IFT) between crude oil and ASP solution is the main mechanism in ASP flooding. Evaluating IFT between crude oil and ASP solution is a key parameter for ASP flooding in laboratory experiments or field projects. In order to obtain good result of ASP flooding in the reservoir in Zahra field, the influence of the concentration of Na₂CO₃ on IFT between Zahra crude oil and ASP solution with three different surfactants, BHJC, SS-231, and SS-233, was researched. IFT was measured with surface tension meter SVT20N, Dataphysics Co. Germany, at 72°C. For the view of IFT result anionic surfactant BHJC is more suitable for the Zahra oil field. This research is helpful for practical application of ASP flooding in Zahra oil field.     

The Effects of Oil Displacement Efficiency and Conformance Efficiency on Viscosity of ASP Flooding in a Heterogeneous Reservoir

According to the formation conditions of alkali/surfactant/polymer (ASP) flooding in Daqing oilfield, the effects of the concentrations for polymer and alkali in ASP solution on oil recovery efficiency were studied by means of oil displacement experiments and numerical simulation. The effects on improving oil recovery by different ASP solution have been investigated from the aspects of interfacial characteristics and rheological behavior. Only the apparent viscosity of ASP solution reaches the critical viscosity, the ultralow interfacial tension can play an important role in enhanced oil recovery. Both displacement experiments and numerical simulation shows that ASP solution has a critical viscosity to certain heterogeneity.     

复合体系超低界面张力和碱在驱油过程中的实际作用

以物理模拟实验结果为依据并结合理论分析发现,在实际油藏的驱油过程中,础活性剂／聚合物（ASP）复合体系与原油的超低界面张力对于启动残余油滴和降低毛管阻力的作用均比以往所推断的要小;为使油／水界面张力达到超低而加入的大量强碱,将导致储层矿物的溶蚀、地层和井筒的严重结垢以及产出液的深度乳化,这对于复合驱的总体效果和效益都是不利的。因此,对于复合体系超低界面张力和碱在驱油过程中的实际作用研究应予以客观的评价,对于非超低界面张力体系驱油实际效果的研究应引起足够的重视.     

STUDYING THE INTERACTIONS BETWEEN AN ARABIAN HEAVY CRUDE OIL AND ALKALINE SOLUTIONS

An experimental study to examine the effectiveness of alkaline flooding for the recovery of an Arabian heavy crude oil is presented. The interfacial tension (IFT) behavior of crude oil/alkali systems over a wide range of parameters (pressure, temperature, alkali concentration and time) was studied. These alkaline reagents react with the acidic species in crude oil to form surface-active soaps in-situ. This leads to a lowering of interfacial tension (IFT) and subsequently the mobilization of residual oil. The equilibrium IFTs obtained through alkaline flooding are compared with the IFTs when a synthetic surfactant (dodecyl benzene sulfonic acid sodium salt) is used in EOR recovery. A mathematical model representing the complete chemistry of the transient process is also presented. The model consists of a set of differential equations describing reactions, diffusion, and adsorption at the oil/alkaline solution interface. The kinetic parameters in the model are obtained through a differential algebraic optimization technique. The concentration of the surface active species are related to the measured IFTs through an independent step that is based on isolating the surface active species formed by the reaction between the acids in the crude oil and the alkaline solution. A sensitivity analysis using the model is carried out to study the effect of surface potential and alkaline concentration on the transient interfacial tensions.     

用中和烃氧化产物制备高界面活性的驱油剂

为了用C_(22)和C_(26)直链和环烷烃的石油馏分油作原料制备适用于强化采油的活性剂,先将原料汽相氧化,再用碱液中和氧化产物。用红外光谱研究了氧化产物和中和产物的组成,发现前者含有羧酸,后者含有羧酸盐。得到的羧酸盐活性剂用于模拟油[由38.8%(体积)的异丙苯和61.2%(体积)的正癸烷组成],使油水间达到低于10~(-2)mN/cm的超低界面张力。实验表明,用氢氧化钠进行中和,比用其他的碱性物质(如硅酸钠、三聚磷酸钠、碳酸钠)更易得到界面活性高的活性剂溶液;当硅酸钠或三聚磷酸钠协同氢氧化钠一起与氧化产物反应时,所得活性剂的界面张力对电解质浓度的敏感程度比仅用氢氧化钠作处理剂时低,中和时的碱量会影响所得活性剂体系的界面张力。对于活性剂浓度不同的体系,若pH值相同则最佳含盐量也相同;若pH值高,则最佳含盐量低。当活性剂体系含有1000ppm的氯化钙时,仍具有良好的界面活性。在驱油试验中,浓度为1%的1个孔隙体积的活性剂溶液可采出42%的二次残油。     

化学驱中动态界面张力现象对驱油效率的影响

本文测定了两种原油在不同化学驱配方下的油／水动态界面张力变化。通过一系列驱油效率实验，研究了动态界面张力最低值，稳态值，油、水相粘度的变化对驱油效率的影响。实验结果表明：动态界面张力平衡值的大小控制岩心驱替过程化学驱段塞提高采收率的能力。如果仅仅动态界面张力最低值达到超低，将难以获得高的采收率。在含有聚合物的复合驱中，由于协同效应的存在，启动残余油所需的界面张力值不必要达到１０＾－３ｍＮ／ｍ。聚合