Molecular design and applications of a nanostructure green Tripodal surface active ionic liquid in enhanced oil recovery: Interfacial tension reduction, wettability alteration, and emulsification

Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tripodal imidazolium SAIL as an environmentally-friendly substitute to the conventional surfactants. The product has a star-like molecular structure centered by a triazine spacer, namely [(C_(4)im)_(3)TA][Cl_(3)], prepared by a one-step synthesis method and characterized with FT-IR, NMR, XRD, and SEM analysis methods. The interfacial tension of the system was decreased to about 78% at critical micelle concentration of less than 0.08 mol·dm^(−3). Increasing temperature, from 298.2 to 323.2 K, improved this capability. The solid surface wettability was changed from oil-wet to water-wet and 80% and 77% stable emulsions of crude oil–aqueous solutions were created after one day and one week, respectively. Compared to the Gemini kind homologous SAILs, the superior effects of the Tripodal SAIL were revealed and attributed to the strong hydrophobic branches in the molecule. The Frumkin adsorption isotherm precisely reproduced the generated IFT data, and accordingly, the adsorption and thermodynamic parameters were determined.

Eco-friendly calcium alginate microspheres enable enhanced profile control and oil displacement

Polymer microspheres(PMs),such as polyacrylamide,have been widely applied for enhanced oil recovery(EOR),yet with environmental concerns.Here,we report a microfluid displacement technology containing a bio-based eco-friendly material,i.e.,calcium alginate(CaAlg)microspheres for EOR.Two dominant mechanisms responsible for EOR over Ca Alg fluid have been verified,including the microscopic oil displacement efficacy augmented by regulating capillary force(determined by the joint action of interfacial tension and wettability between different phases)and macroscopic sweep volume increment through profile control and mobility ratio reduction.This comprehensive effectiveness can be further impacted when the CaAlg microsphere is embellished ulteriorly by using appropriate amount of sodium dodecyl sulfonate(SDS).The core flooding and nuclear magnetic resonance(NMR)tests demonstrate that CaAlg-SDS microsphere can balance the interphase property regulation(wettability alteration and IFT reduction)and rheology properties,enabling simultaneous profile control and oil displacement.Excessive introduction of SDS will have a negative impact on rheological properties,which is not favored for EOR.Our results show that the involvement of 4-m M SDS will provide the best behavior,with an EOR rate of 34.38%.This cost-effective and environmentally-friendly bio-microspherebased microfluidic displacement technology is expected to achieve“green”oil recovery in future oilfield exploitation.

Study of Oil/Water Interfacial Tension of Vacuum Residual Fractions from Iranian Light Crude Oil

The vacuum residual from Iranian Light crude oil are separated into a series of 16 narrow fractions according to the molecular weight by the supercritical fluid extraction and fractional (SFEF) technology. The chemical element and the UV spectrum of each fraction are analyzed. The effects of several factors on the interfacial tension are investigated, which are the fraction concentration in oil phase, the ratio of oil component, the salts dissolved in the water phase and the pH value. The interfacial tension decreases rapidly as the concentration of the residual fraction in the oil increases, showing a higher interfacial activity of the fraction. The interfacial tension changes, as the amount of absorption or the state of the fractions in the interface changes resulting from different ratios of oil, different kinds or concentrations of salts in water, and different pH values. It is concluded that the interfacial tension changes regularly, corresponding to the regular molecular parameters of the vacuum residual fractions.

The role of CO2 and ion type in the dynamic interfacial tension of acidic crude oil/carbonated brine

The e ects of CO2 and salt type on the interfacial tension(IFT) between crude oil and carbonated brine(CB) have not been fully understood. This study focuses on measuring the dynamic IFT between acidic crude oil with a total acid number of 1.5 mg KOH/g and fully CO2-saturated aqueous solutions consisting of 15,000 ppm of KCl, NaCl, CaCl2 and MgCl2 at 30 °C and a wide range of pressures(500–4000 psi). The results of IFT measurements showed that solvation of CO2 into all the studied aqueous solutions led to an increase in IFT of acidic crude oil(i.e., comparison of IFT of crude oil/CB and crude oil/brine), while no significant e ect was observed for pressure. In contrast, the obtained results of studied salts indicated a positive e ect on the IFT reduction of acidic crude oil/carbonated water(CW)(i.e., comparison of IFT of crude oil/CB and crude oil/CW).

A novel nanofluid of modified carbon black nanoparticles for enhanced oil recovery in low permeability reservoirs

A novel nanofluid of modified carbon black(MCB)nanoparticles was initially developed for enhanced oil recovery(EOR)in low permeability reservoirs.The MCB nanoparticles were obtained via a three-step reaction involving modification by oxidation,acyl chlorination,and activated grafting.MCB nano-particles were spherically dispersed,with an average size of 72.3 nm.Compared with carbon black(CB)nanoparticles,dispersed MCB nanoparticles can effectively reduce the oil-water interfacial tension(IFT)to 10^(-2)mN/m and change the surface wettability of sand particles.Based on the results of core flooding experiments,the MCB nanoparticles exhibited a better EOR capacity than surfactants and CB nano-particles,and the final oil recovery was significantly increased by 27.27%.The core scanning test showed that the MCB nanoparticles could plug high permeability channels by adsorbing onto the surfaces of sand particles and forming larger aggregates that bridge across pores or throats,resulting in a higher swept volume.The synergistic effects of improved swept volume and oil displacement efficiency were the EOR mechanisms of the MCB nanoparticles.The studies indicate that these MCB nanoparticles have excellent potential for EOR in low permeability reservoirs.

表面活性剂对水驱普通稠油油藏的乳化驱油机理

为了研究乳化降黏驱油剂对不同渗透率的水驱普通稠油油藏的驱油效率和孔隙尺度增效机理,选取了烷基酚聚氧乙烯醚(J1)、α-烯基磺酸盐类表面活性剂(J2)、十二烷基羟磺基甜菜碱(J3)、J3与烷基酚聚氧乙烯醚羧酸盐复配表面活性剂(J4)作为驱油剂,开展了4种驱油剂一维驱油和微观驱油模拟实验,明确了乳化降黏驱油剂在孔隙尺度的致效机理。结果表明,降低界面张力对提高驱油效率的作用大于提高乳化降黏率。在油藏条件下,乳化降黏驱油剂需要依靠乳化降黏和降低界面张力的协同增效作用,才能大幅提高驱油效率。乳化降黏驱油剂的乳化能力越强、油水界面张力越低,驱油效率增幅越大。当化学剂乳化降黏率达到95%时,油水界面张力从10^(-1)mN/m每降低1个数量级,化学剂在高渗透和低渗透岩心中的驱油效率依次提高约10.0%和7.8%。乳化降黏驱油剂注入初期通过降低界面张力,使得高渗透岩心和低渗透岩心中的驱替压力分别为水驱注入压力的1/2和1/3,从而提高注入能力。注入后期大块的原油被乳化形成大量不同尺寸的油滴,增强原油流动性,提高驱油效率。乳化形成的界面相对稳定的稠油油滴,能暂堵岩石的喉道和大块稠油与岩石颗粒形成的通道。油滴的暂堵叠加效应,使高渗透和低渗透岩心的驱替压差分别为水驱压差的5.2倍和32.3倍,大幅提高了注入压力,从而扩大平面波及面积。降黏驱油剂驱油实现了提高驱油效率的同时扩大波及范围。研究结果为水驱稠油开发用驱油剂的研发提供参考,为大幅提高水驱普通稠油采收率奠定基础。

Adsorption of Natural Surfactant on Sandstone in Enhanced Oil Recovery: Isotherms and Kinetics Studies

In chemical enhanced oil recovery, surfactants are injected into the reservoir with the intention to lower interfacial tension (IFT) between the water and oil phases, and thereby bring about efficient displacement of oil. However, the adsorption of the surfactants to reservoir rock surfaces leads to the loss and reduction in concentration of the surfactants, which in turn reduces the overall efficiency of the oil recovery process, with attendant financial losses. In this work, the adsorption of Quillaja Saponaria (QS), a novel, natural, non-ionic surfactant, on crushed sandstone reservoir rock is investigated. X-ray diffraction (XRD) study of clean sandstone particles has been undertaken to determine the main components present in the sand particles. The conductivity method was used to measure CMC and the surfactant concentrations in aqueous solutions. Batch adsorption experiments were used to determine the amount of QS adsorbed on rock surface. Equilibrium conditions were reached after almost 5 days. From the results of the study, the Langmuir isotherm model is more suited for predicting the adsorption behaviour of QS on sandstone. The kinetic adsorption of QS obeys the pseudo-second order model. This study is particularly relevant in surfactant selection for chemical EOR processes.

纳米生物质体系性能评价及驱油特性实验研究

本文以玉米秸秆与纳米硅为原料,制备了改性纳米生物质,并评价了其在不同条件下的表面活性及界面张力。通过调整纳米生物质浓度(0.1%~1.0%)、注入速度(0.1~1.0mL·min^(-1))及注入体积(100~1000mL),优化体系的驱油参数。结果显示,纳米生物质浓度为0.8%、注入速度为0.6mL·min^(-1)、注入体积为600mL时,体系表现出最佳的驱油效率。此外,实验室结果在典型油田的现场应用中得到验证,应用优化后的体系参数,油田的日产油率从100桶提升至140桶,增幅达40%。由此可见,纳米生物质体系能够提高油田驱油效率,研究成果有助于指导油田开发中生物质材料的应用。

氟表面活性剂的合成及油田应用的最新进展(续完)

1.5 gemini型氟表面活性剂.gemini表面活性剂因其独特的化学结构而广受关注。传统表面活性剂为单头单尾,而gemini表面活性剂则是双头双尾,头基间通过间隔基连结。gemini表面活性剂的物理化学性质包括较低的cmc和高于单体(常规)表面活性剂的表面性能。为寻找长碳氟链氟表面活性剂的替代品,Du等合成了一系列含有全氟醚链的gemini表面活性剂,并对其表面张力进行了研究。采用酰胺化反应和季铵化反应两步合成了gemini表面活性剂。在第1步中,N,N-二甲基-1,3-丙二胺分别与氟化酯或酰氟反应生成氟化酰胺中间体。第2步,该中间体与二溴化物反应,通过季铵化得到gemini表面活性剂(图17)[46]。

烷基糖苷和醇醚糖苷对辽河稠油的界面张力的影响研究

利用旋转滴界面张力仪,研究了在增加环氧乙烷基团(EO)的情况下,烷基糖苷与醇醚糖苷单独使用对正构烷烃及辽河原油之间的界面张力的影响、在复合体系下对界面张力的影响;考察了表面活性剂质量分数、一价与二价离子浓度和EO基团对体系动态界面张力的影响。结果表明,两种糖苷型表面活性剂可以与十二烷基苯磺酸钠产生较强的协同作用,同时EO链可以调节表面活性剂的亲水亲油平衡值,使得表面活性剂在界面处排列更紧密;矿化度的增加可以压缩双电子层,使得界面处分子紧密排布,降低界面张力。在适当的矿化度条件下,复配表面活性剂系统可以与辽河稠油间产生超低界面张力。

纳米流体提高采收率机理研究现状

与传统的表面活性剂和聚合物溶液相比,纳米流体驱油是一项新的提高采收率技术,但目前机理研究成果较为分散,缺少系统性。因此,结合国内外纳米流体研究情况,总结纳米流体主要提高采收率机理,指出了纳米流体目前所面临的研究难点,展望了纳米材料在今后的攻关方向。研究表明:纳米流体提高采收率机理包括降低油水界面张力,在油水固三相区形成楔形膜,产生结构分离压力,改善流度比扩大波及体积,改变岩石润湿性,增强泡沫稳定性,降低注入压力和选择性调堵孔道;今后可从提高纳米流体稳定性、降低纳米流体成本、提高采收率机理协同性研究以及开发高效纳米驱油体系等方面进行深入探索。该研究为大规模推广纳米流体在提高采收率方面的应用提供了理论基础和实验依据。

CO_(2)响应型β-环糊精材料用于稠油降黏

制备了一种环境友好型马来酸酐改性β-环糊精(MAH-β-CD),温和条件下将其与聚醚胺(JD230)通过静电作用合成了具有CO_(2)响应性的表面活性剂(MJD230)。MJD230能与稠油形成稳定的水包油乳液,进而有效降低溶液的表面张力。在CO_(2)调控下,MJD230可重复用于稠油的乳化降黏和破乳。利用FTIR对MJD230结构进行了表征。通过观察降黏率和乳液粒径优化MJD230的合成条件,同时对降黏效果和乳液的稳定性进行了考察。将在反应温度为60℃,反应时间为60min,MAH-β-CD与JD230物质的量比为2∶1条件下制备的MJD230配成质量分数为0.5%的MJD230水溶液,其与稠油按照体积比为3∶7乳化后,稠油降黏率可达99.19%。反应体系pH和电导率的可逆变化证明了MJD230溶液对CO_(2)的响应性,这为表面活性剂驱油和CO_(2)捕集相结合提高稠油采收率提供了可行的途径。

烷基羧酸甜菜碱驱油机理研究

为了探究不同甜菜碱的微观驱油机理,文章选取三种具有不同疏水烷基链长度的羧酸甜菜碱表面活性剂进行微观可视化驱油实验,并测定了界面张力和乳化性能。实验结果表明,烷基羧酸甜菜碱能够高效降低油水界面张力,促进原油原位乳化。随着烷基链长增加,界面张力进一步降低,乳化效果增强。十六烷基羧酸甜菜碱提高采收率机制包括以下两个方面:0.3%C16BC可以将界面张力降至10^(-2)mN/m数量级,通过乳化和弱剪切作用有效启动孔道中原油,将柱状、多孔和簇状剩余油分解形成水包油乳化油滴,提高洗油效率。同时,由于乳化油滴产生的贾敏效应叠加,C16BC可产生稳定的堵塞通道效果,使残余油的水相波及效率提高了20%。C16BC作为一种可以原位乳化协同自调剖的驱油剂,驱油效率较地层水驱提高42%以上,可以用于低渗油藏化学驱提高采收率。

驱油流体吸附抑制剂的合成与评价

目的在化学驱的实施过程中,地层对驱油剂的吸附滞留是表面活性剂进入地层后含量损失的一种主要原因,为了减少驱油流体在地层的损耗成本而展开对驱油液体吸附抑制剂的研究。方法以二氰二胺(DCD)、1-十八胺盐酸盐(OHC)为原料,基于亲核加成的原理采用熔融法在150℃下合成了一种针对驱油流体的吸附抑制剂OHCB,该表面活性剂同时具备强疏水基、强极性原子和阳离子基团,因此具有较强的占据黏土矿物表面吸附位点的能力。对其进行了红外吸收、紫外吸收、元素分析、质谱等结构表征,采用静态吸附法研究了其作为添加剂的最佳配比,并验证在最佳配比下对驱油剂AEO7的吸附抑制效果,以及该体系相较AEO7单一体系的静态洗油效率、乳化性及润湿性的变化。结果OHCB抑制驱油剂AEO7在黏土矿物表面的吸附效果较好,在驱油剂与吸附抑制剂质量比为5∶1的情况下,抑制效果可达27%以上。结论OHCB不仅具有较好的吸附抑制效果,且其加入使AEO7的静态洗油效率提升至27.3%、γc m c降至27.1 mV/m,CMC降至38 mg/L、油-水界面张力降至0.5 mV/m以下,对体系性能起到了协同增效的作用,并且相较于需要预吸附的牺牲剂,其使用更为便捷。

应用OP-13复配型表面活性剂降黏实验研究

研究了以乳化剂OP-13作为主剂,与不同种类的阴离子和碱复配的三元复配体系对稠油的乳化降黏性能。结果表明,阴离子表面活性剂中质量分数为0.5%的SAS60与质量分数为0.6%的OP-13复配后,降黏效果最优,降黏率96.3%,分水率38%。三元复配体系中,OP-13、SAS60、叔丁醇钠以质量比6∶5∶3进行复配时,降黏性能最好,降黏率98.3%,分水率为1%。

偏远井场油水分离与原油降凝技术研究

为解决延长油田部分偏远井场含水原油在井场脱水困难,冬季原油凝固流动性差外运难的问题,开展破乳剂类型、温度、浓度影响的破乳特性实验、微观形貌采集以及降凝流变特性实验,寻求高效脱水与降凝方案,通过实验结果制定生产改造方案实现高效脱水与降凝。研究表明井场破乳脱水与降凝的关键在于药剂与产液的充分融合,同时破乳剂的加入使活性水的界面张力明显下降,浓度为100ppm时,活性水的界面张力达到了最低值。通过微观形貌观察,随着破乳剂浓度的增加,油滴的粒径先增大后减小,油滴分布先稀疏后密集,在浓度为100ppm时油滴的粒径达到最大,此时界面张力最低,活性较高,破乳剂能够快速取代天然表面活性物质,导致原油破乳,破乳率达到97%以上。当破乳后未加降凝剂时原油最优热处理温度在60至70℃之间,添加浓度为150ppm的J2降凝剂,加热至50℃,凝点降低至-2~4℃。

扶余致密油藏CO_(2)吞吐参数优化设计

为解决致密油开采初期产量递减快、采收率低的问题,结合扶余致密油藏岩石和流体性质,采用数值模拟方法,研究了注入时机、注入压力对CO_(2)吞吐采油效果的影响,优化工程参数,分析了致密油CO_(2)吞吐过程中的油藏压力分布特征、界面张力分布特征以及致密油CO_(2)吞吐开发的可行性。研究表明:油层压力系数降至0.65左右时开展CO_(2)吞吐,CO_(2)可与原油充分接触,有利于发挥CO_(2)原油溶解作用,提高开采效果;注入压力接近最小混相压力时,CO_(2)以游离相进入基质,更易进入基质深处,与致密油充分接触,并在原油中溶解混相,改善开发效果。溶解平衡后,CO_(2)与致密油界面张力随时间快速增加,以此确定闷井时间。研究确定了CO_(2)吞吐采油最佳工程参数,即注入量为8000 t,注入速度为120 t/d,注入压力为27 MPa,闷井时间为30 d,计算该方案下增油量为3084 t,换油率为0.39。水平井现场试验也证明CO_(2)吞吐技术应用于扶余致密油藏,采收率提高了1.38~3.33个百分点。研究结果对拓展致密油藏CO_(2)吞吐开采技术的应用具有重要意义。

SIAPES的合成及低温油藏原位乳化驱油体系构建与性能

W/O型乳液驱油是一项有效提高老油田采收率技术。但低温条件下常用的乳化体系不能同时满足形成W/O型乳液和降低界面张力。本文合成并表征了异构十三醇聚氧乙烯醚磺酸钠(SIAPES),并与椰子油烷基二乙醇酰胺(CEDA)复配构建了低温油藏原位乳化驱油体系,评价了体系的乳化性能、降低了油水界面张力并改善了岩石润湿性能力。同时利用在线NMR驱替系统揭示了原位乳化驱油体系在低温油藏条件下提高采收率的潜力。结果表明:原油-地层水自乳化相变点为60%,利用原位乳化驱油体系对油水自乳化进行干预后,乳液相变点提高到65%,且发生相变后乳液黏度明显高于自乳化乳液的黏度,流度控制能力增强;原位乳化驱油体系能将油水界面张力由12.00 mN/m降低至0.12 mN/m,改善亲油岩心润湿性至亲水;在渗透率级差为12,水驱至经济极限的条件下,0.6 PV的原位乳化驱油剂驱和后续水驱使采收率提高了26.8%。

驱油用纳米材料在提高采收率方面研究进展

随着对石油资源需求不断上升和开采难度不断增加,提高采收率的技术需要不断创新,纳米材料作为一种新型材料,由于具有纳米尺寸和独特晶界结构,导致其具有独特的性质,在提高采收率方面具有很大的潜力。本文系统综述了纳米材料在提高采收率方面的作用机理,包括降低表/界面张力,增加毛细管数;结构分离压力作用,微观展示石油从岩石上剥离;改变润湿性,加强水渗吸作用;增强乳液和泡沫稳定性从而增强体系稳定性;改善流度比增加体积波及效率;抑制沥青沉积,催化沥青分解,防止孔隙堵塞和减少地层伤害;抑制颗粒运移、减少地层伤害等。列举了纳米材料在低渗透油藏、稠油油藏和高含水油藏等条件下提高采收率的矿场案例,指出了纳米材料的油田规模化应用所面临的挑战。

界面性质对表面活性剂洗油效率影响研究

表面活性剂通过改变油-水-岩石界面性质,可以提高稠油流动能力,促进采收率的提高。然而,界面相互作用力的改变对洗油效率和采收率的影响难以精确量化。提出了一种激光共聚焦成像及图像处理的方法分析洗油前后原油的分布,并计算洗油效率。实验及计算结果显示,界面张力对洗油效率的影响较小,而系统润湿性和黏附功的影响更为显著。黏附功结合了表活剂对界面张力和润湿性的影响,是表活剂评价和筛选的一个重要参数。另外,固体表面的润湿反转使得表活剂的洗油效率随时间发生了改变。将洗油实验和激光共聚焦成像及图像处理相结合,精确计算了洗油效率,揭示了界面性质对洗油效率的影响,对化学驱提高稠油采收率具有重要指导意义。