高盐油藏下Gemini/阴-非离子表面活性剂协同效应研究

研究了阳离子双子表面活性剂12-N-12与阴-非离子型表面活性剂W950混合体系与原油作用后的界面张力,结果表明:单独使用其中一种仅能使界面张力降低至10-2m N/m,而将两者一同使用后可产生较好的协同作用,且在W950与12-N-12摩尔比为(4∶1)~(1∶1.5)、总浓度为0.1%~0.2%的条件下与原油作用,可快速形成超低界面张力。对该复合型表面活性剂的耐温耐盐情况进行了相关测试,试验结果表明:该复合体系于高矿化度地层水中可形成相对稳定的溶液,在Ca2+,Mg2+离子质量浓度达到1 000 mg/L时仍能达到10-3m N/m的界面张力;抗温测试方面,升高溶液温度(30~65℃)会使界面张力进一步下降。综合研究表明,该体系满足高温高盐油藏提高采收率的需求。     

耐盐型双子表面活性剂驱油体系研究

对一种新型双子表面活性剂GA12-4-12进行了研究。该表面活性剂在矿化度为2.5×10^5mg/L、氯化钙浓度为1.5×10^4mg/L的水溶液中表现出良好的表面活性,其临界胶束浓度为538.6mg/L。GA12-4-12溶液与稀油间的油水界面张力随着盐含量的增加（60～250g/L）而降低。在高矿化度模拟地层水条件下,GA12-4-12及其与聚合物复合体系SP的油水动态界面张力均能达到超低值（10^-3mN/m）。进行模拟驱油实验表明,GA12-4-12与SP复合体系提高水驱采收率分别为6.25%、10.67%。     

阴离子/非离子表面活性剂驱油技术研究

对上海石油化工研究院研制的阴离子/非离子表面活性剂进行了相关方面的适用性评价,通过岩心模拟驱替实验研究了改善驱油效果的能力。评价结果表明:该表面活性剂与明15块注入水具有良好的配伍性;降低界面张力能力显著,推荐使用的浓度范围为0.05%~0.30%;地层温度条件下,可稳定65 d;65℃时经过150 min达到析水平衡且析水率仅为60%,乳化能力较好;吸附量均在2.0 mg/g左右,抗吸附能力良好。模拟驱替实验表明:使水驱采收率提高约12%,最终采收率达到42%,驱油效率显著,具有较好的经济效益。     

复配表面活性剂对复合驱油体系性能影响研究

通过对α-烯烃磺酸盐、重烷基苯磺酸盐、石油磺酸盐和复配型等4种表面活性剂配制复合驱油体系的界面张力和黏度性质进行评价,重点对复配型表面活性剂配制复合驱油体系的界面张力和驱油效果进行了系统评价。结果表明,当碱的质量分数为0.3%~0.9%、表面活性剂的质量分数为0.1%~0.3%时,复配型表面活性剂配制复合驱油体系的界面张力可以达到10-3mN/m数量级,且具有达到超低界面张力所需质量分数低和范围宽等特点。物理模拟实验表明,复配型表面活性剂配制三元复合体系的增油效果较单一类型表面活性剂配制三元复合体系的好,采收率增加1.46%(体积分数)。在此基础上,对复配表面活性剂超低界面张力的作用机理进行了理论分析。     

驱油表面活性剂体系优选研究

表面活性剂驱可以有效地提高洗油效率,减少毛细管阻力,对低渗油藏提高采收率达到理想的效果。利用界面张力仪评价了4种表面活性剂(甜菜碱活性剂、羧酸盐活性剂、石油磺酸盐SS活性剂、DVS活性剂)界面张力稳定性幵优选出了2种(界面张力达到了10~(-3) mN/m)。基于优选的2种表面活性剂迚行了其乳化性能的评价,以达到更好的驱油效果。     

阴离子表面活性剂复配体系的匀染性能研究

当烷基聚氧乙烯醚磷酸酯钾、缩甲醛四烷基萘磺酸钠、十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠及蓖麻油硫酸化钠的质量比为2．0：1．0：1．3：1．0：1．0时，对羊毛匀染性具有最佳效果，在pH为1的酸性溶液中稳定。与国外同类产品进行比较，在纯水和染浴中的渗透时间及起泡消泡性基本相当，分别是1．2min～1．3min和1．3min～1．4min(参照物)；起泡性分别是2mL～6mL和1．5mL～5．0mL(参照物)；消泡性分别为0．5mL～3．5mL和0mL～3mL(参照物)。同等条件下，该混合物的表观色深值和色差值分别为29．4和0．72，参照物分别为23．60和1．82。表明上述阴离子表面活性剂之间具有良好的协同效应，其混合物对羊毛上染具有好的匀染性和较高的上染率。     

超低渗透油藏降压驱油表面活性剂驱技术

针对姬塬油田超低渗透油藏注入压力高,常规酸化及酸压等措施有效期短,且可能造成储层二次伤害的问题,根据L1区油藏地质特征,研发了一种具有很强的分散性、耐温、耐盐性的降压驱油表活剂JZ-01。通过室内实验评价了JZ-01界面活性、润湿性、吸附性、抑制黏土膨胀性、阻垢性及自发渗析性能,结果表明:JZ-01降压驱油活性剂具有较高的界面活性和改变储层润湿性能力,并具有一定的抑制黏土膨胀能力和防垢能力,以及较好的降压驱油应用潜力。通过在L1区现场试验4个临界高压井组,注水井较前期压力上升变缓,对应油井达到了控水增油效果。研究证明JZ-01表活剂具有降压驱油作用,对姬塬油田超低渗透油藏提高采收率具有重要意义。     

表面活性剂及其复配体系

本文主要介绍了表面活性的种类、特性以及复配方法。并着重介绍了复配体系的复配方法、性能以及应用用于学习交流。     

阴／非离子复合表面活性剂驱油剂的制备研究

研究了阴离子表面活性剂AES与非离子表面活性剂OP-10和阴离子表面活性剂AES与非离子表面活性剂TX分别以不同比例混合后对表面／界面张力的影响,并从机理上进行了相关探讨。实验结果表明：当AES与OP-10和AES与TX的质量比分别为8：2和6：4时,表面／界面张力均降低至最低值。二者比较来看,AES与TX的复配体系较AES与OP-10的复配体系降低表面／界面张力的效果明显。     

阴非离子型Gemini表面活性剂驱油体系性能评价

为提高低渗透油藏采收率,开发了一种阴非离子型Gemini表面活性剂ANG7-Ⅳ-7,并测定体系的界面张力、乳化性能和吸附量。结果表明,ANG7-Ⅳ-7表面活性剂浓度在1⁴ g/L范围内,油水界面张力均可达到10-3m N/m的超低数量级,当ANG7-Ⅳ-7浓度为4 g/L时,能使油水界面张力达到最低值6.025×10-3m N/m;在注入浓度为4 g/L时,表面活性剂在油砂上的吸附量为2.035 mg/g。室内岩心驱油试验结果表明,4 g/L的ANG7-Ⅳ-7表面活性剂驱可在水驱后提高采收率11个百分点。     

Preparation and Characterization of an Anionic Gemini Surfactant for Enhanced Oil Recovery in a Hypersaline Reservoir

A new type of anionic Gemini surfactant (AGS) was designed and prepared by a simple, low–cost, and green method, and its properties were characterized. The results showed that the values of parameters such as critical micelle concentration (CMC) value, Γmax, Amin, and pC20 of AGS were 0.10 mmol L⁻¹, 1.62 mmol m⁻², 1.02 nm², and 4.60, respectively, indicating that AGS is highly surface active. AGS has a very good synergistic effect with lauryl diethanol amide (6501), and the mixture surfactant 6501DA (composed of AGS and 6501 with a mass ratio of 1:2.5) has good wetting and emulsifying ability of the crude oil and good resistance to calcium and magnesium ions. In the temperature range from 50 to 70 °C, salinity of 20,000–50,000 mg L⁻¹ of the simulated formation water, and dosage of 6501DA from 500 to 3000 mg L⁻¹, all the interfacial tension (IFT) values between the 6501DA solution and Bamianhe crude oil were lower than 10⁻² mN m⁻¹, and all the adsorption amounts of oil sand to 6501DA in solution were less than 2 mg g⁻¹, indicating that AGS has potential for application in EOR in a hypersaline reservoir.     

Micellization of Anionic Sulfonate Gemini Surfactants and Their Interactions With Anionic Polyacrylamide

Anionic sulfonate gemini surfactants 8‐s‐8(SO₃)₂ and 12‐s‐12(SO₃)₂ (s = 3, 6) were synthesized, and their micellization in aqueous solution at 25.0 °C and pH 9 was investigated. The results show that the critical micelle concentrations (CMC) of 8‐s‐8(SO₃)₂ are more than 2 orders of magnitude larger than those of 12‐s‐12(SO₃)₂, but the spacer length has a relatively small impact on the CMC. Moreover, the interactions of n‐s‐n(SO₃)₂ (n = 8, 12; s = 3, 6) with anionic polyacrylamide (PAM) at 25.0 °C and pH 9 were investigated using surface tensiometry, rheolgy, and scanning electron microscopy (SEM). The results indicate that the surface tension and rheological properties of PAM depend on the concentration of n‐s‐n(SO₃)₂. Below the critical aggregation concentration of C₁, surface tension is sharply reduced, the surface tension of n‐s‐n(SO₃)₂/PAM is lower than n‐s‐n(SO₃)₂ alone, but viscosity is almost unchanged with increasing C_{n‐s‐n(SO3)2}. Above C₁, surface tension reduces very slowly until the saturated concentration of C₂ is reached. Above C₂, surface tension rapidly reduces until C_M is attained, suggesting free n‐s‐n(SO₃)₂ micelles begin to form. In the region of C₁–C_M, the viscosity significantly increases. Above C_M, surface tension is basically unchanged and these curves coincide with those of the single surfactant system. Moreover, the viscosity is almost constant. The SEM images indicate that fibrous aggregates are formed below C₁, then transformed into multilayer fibrous aggregates above C₁, and further into fiber‐braided‐structured and spider‐web‐structured aggregates above C_M. The variation of viscosity is closely associated with the transformation of aggregates.     

Synergistic Effects between Anionic and Sulfobetaine Surfactants for Stabilization of Foams Tolerant to Crude Oil in Foam Flooding

In foam flooding, foams stabilized by conventional surfactants are usually unstable in contacting with crude oil, which behaves as a strong defoaming agent. In this article, synergistic effects between different surfactants were utilized to improve foam stability against crude oil. Targeted to reservoir conditions of Daqing crude oil field, China (45 °C, salinity of 6778 mg L⁻¹, pH = 8–9), foams stabilized by typical anionic surfactants fatty alcohol polyoxyethylene ether sulfate (AES) and sodium dodecyl sulfate (SDS) show low composite foam index (200–500 L s) and low oil tolerance index (0.1–0.2). However, the foam stability can be significantly improved by mixing the anionic surfactant with a sulfobetaine surfactant, which behaves as a foam stabilizer increasing the half-life of foams, and those with longer alkyl chain behave better. As an example, by mixing AES and SDS with hexadecyl dimethyl hydroxypropyl sulfobetaine (C₁₆HSB) at a molar fraction of 0.2 (referring to total surfactant, not including water), the maximum composite foaming index and oil tolerance index can be increased to 3000/5000 L s and 1.0/4.0, respectively, at a total concentration between 3 and 5 mM. The attractive interaction between the different surfactants in a mixed monolayer as reflected by the negative β^s parameter is responsible for the enhancement of the foam stabilization, which resulted in lower interfacial tensions and therefore negative enter (E), spreading (S), and bridging (B) coefficients of the oil. The oil is then emulsified as tiny droplets dispersed in lamellae, giving very stable pseudoemulsion films inhibiting rupture of the bubble films. This made it possible to utilize typical conventional anionic surfactants as foaming agents in foam flooding.     

碳氟-碳氢表面活性剂复配性能研究

测定了新型非离子氟碳表面活性剂Intechem-01与α-烯烃磺酸盐(AOS-201)复配溶液性能,结果显示出两者之间很好的协同效应。复配后溶液表面张力维持较低水平,cmc低达1.6×10-3(wt%),油水界面张力<1.8mN.m-1,从而可以在油面上更好铺展;同时表现出特有的泡沫性能。     

耐温表面活性剂在油藏开发中的研究进展

表面活性剂驱是三次采油中稳产增产的重要手段,随着高温油藏研究开发的不断深入,耐高温表面活性剂具有更加重要的研究价值。该文根据深层油藏温度高的特点和中国油藏开发现状,在研究国内外文献资料的基础上,将具有耐高温性能的表面活性剂按阴-非离子型(Anionic-nonionic)、两性型(Amphoteric)、双子型(Gemini)和氟碳型(Fluorocarbon)分类。通过对4类表面活性剂的比较,讨论了基团、分子结构等因素对表面活性剂耐温性的影响,指出可生物降解表面活性剂是耐温表面活性剂继续发展的重要方向,同时对双子表面活性剂的合成及氟碳表面活性剂的应用提出了建议。     

高分子表面活性剂与原油形成超低界面张力的研究

对ＡＭ－ＡＯＰ_ｎ和ＣＭＣ－ＡＲ１２ＥＯ_ｎ两类高分子表面活性剂与原油形成超低界面张力的研究结果表明,加碱复配后,ＡＭ－ ＡＯＰ_ｎ和 ＣＭＣ－ ＡＲ_１２ＥＯ_ｎ与大庆原油的界面张力分别可达 ２．６ ×１０~（－３）ｍＮ／ｍ和 ３．２ｘ １０~（－３）ｍＮ／ｍ。显微观察表明,碱使胶束解缔是界面张力降低的主要因素。     

三元复合体系界面张力的影响规律研究

以河南双河油田为研究对象,以吸附理论和扩散理论为基础,利用物理模拟实验通过分析碱和表活剂对界面张力的影响,进一步探究了三元复合体系中协同效应对油水界面张力的影响,最后通过数值模拟技术验证了不同碱浓度对三元复合体系降低油水界面张力的影响,提高了实验研究成果在实际矿场应用中的可靠性和准确性。结果表明,三元复合体系的协同效应能有效降低油水界面张力,其中聚合物主要延长起到超低界面张力时间的作用,但不影响平衡界面张力值,表面活性剂和碱主要起到降低平衡界面张力最低值的作用。     

Surface Properties and Solubility Enhancement of Anionic/Nonionic Surfactant Mixtures Based on Sulfonate Gemini Surfactants

As a class of novel surfactants, Gemini surfactants usually exhibit fairly excellent interfacial properties in aqueous solutions on account of the unique structure. They have significant application and development potential for industrial production. However, the mixing properties of Gemini surfactants with conventional surfactants are the key to their application. The equilibrium surface tension curves of anionic/nonionic surfactant mixtures based on the sulfonate Gemini surfactant (SGS-12) were measured using the Wilhelmy Plate method. The parameters of surface adsorption, the interaction parameters between anionic and nonionic surfactants, and the thermodynamic parameters of micelle formation were calculated from the corresponding equations. In addition, the dynamic surface tension (DST) curves of anionic/nonionic surfactant mixtures were examined through bubble profile analysis, and the diffusion performance parameters were acquired from empirical formulas. The solubilization of pyrene in micelle solutions was studied using UV–vis absorption spectroscopy. The results show that the interaction parameters of all anionic/nonionic surfactants are negative, indicating that there is a synergistic effect on reducing the surface tension. For the SGS-12/OP-10, SGS-12/Tween 80, SGS-12/AEO9, and SGS-12/APG0810 mixtures, the optimum mixing ratios are 6:4, 7:3, 7:3, and 8:2, respectively. The thermodynamic data of micelles show that the formation of mixed micelles for SGS-12/APG0810 mixtures is an enthalpy-driven process. The tendency of DST curves of the SGS-12/APG0810 mixture is similar to that of SGS-12. In comparison with single-surfactant solutions, the anionic/nonionic surfactant mixtures show stronger solubilization capacity toward pyrene.     

油水界面行为对原油乳状液破乳的影响

测定了在破乳剂作用下原油乳状液的油水界面张力,界面膜强度及破乳脱水率,结果表明,界面张力的变化与体系的初始状态有关,它反映了破乳剂分子在界面上的吸附程度,界面张力的高低不能作为破乳剂破乳效果的依据。具有较强的油水界面吸附能力而又能显著降低界面膜强度的破乳剂分子,能达到较好的破乳效果。     

Dissolution of Soap Scum by Surfactants. Part III. Effect of Chelant Type on Equilibrium Solubility and Dissolution Rate of Calcium and Magnesium Soap Scums in Various Surfactant Systems

Soap scum can be effectively removed by using an appropriate surfactant with a chelating agent at a high solution pH. The equilibrium solubilities and dissolution rates of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were investigated in aqueous solutions containing three different types of surfactants [methyl ester sulfonate (MES) as an anionic surfactant; alcohol ethoxylate (EO9) as a nonionic surfactant; and dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant] in the presence of different biodegradable chelants: trisodium ethylenediamine disuccinic acid (Na₃EDDS) and tetrasodium glutamate diacetic acid (Na₄GLDA) compared with disodium ethylenediamine tetraacetate (Na₂EDTA), a chelant with poor biodegradability. The highest equilibrium solubility and dissolution rate of either soap scum were observed at high pH in the DDAO system with Na₄GLDA. In addition, the calcium soap scum had a similar to higher equilibrium solubility and a higher dissolution rate constant as compared with the magnesium soap scum.