脂肪醇聚氧乙烯醚系列磺酸盐的泡沫性能研究

磺酸盐类阴离子表面活性剂在采油工业中应用广泛,其泡沫性能(起泡性和泡沫稳定性)对采收率影响很大。采用改进的Ross-Miles法对烷基碳数为14、16、18的脂肪醇聚氧乙烯(3)醚磺酸钠(CnH2n 1O(EO)2CH2CH2SO3Na,n=14、16、18)在不同条件下的泡沫性能进行了研究。结果表明,随着疏水基长度增加,表面活性剂起泡性降低,稳泡性增强;十四醇聚氧乙烯(3)醚磺酸钠起泡性最好,十八醇聚氧乙烯(3)醚磺酸钠稳泡性最优;随着温度的上升,3种表面活性剂起泡性增强,稳泡性降低。     

Use of low-temperature differential scanning calorimetry for determination of ethylene oxide content in some nonionic surfactants

Low-temperature differential scanning calorimetry studies on ethoxylates of hydrogenated castor oil and 12-hydroxystearic acid show endothermic transformations that could be ascribed to melting of ethylene oxide (EO) components of the surfactant molecule. The ethoxylation process also results in formation of free polyethylene glycol (PEG). Separation of free PEG followed by area under the curve measurements enabled estimation of EO content of the product formed during manufacture. The melting endotherm provided additional information on the chain-length distribution of polyoxyethylene units in the surfactant.     

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.     

Progress in research of sulfobetaine surfactants used in tertiary oil recovery

The synthesis of sulfobetaine surfactants and their application in tertiary oil recovery (TOR) are summarized in this paper. The synthesis of sulfobetaine surfactants was classified into three categories of single hydrophobic chain sulfobetaine surfactants, double hydrophobic chain sulfobetaine surfactants and Gemini sulfobetaine surfactants for review. Their application in TOR was classified into surfactant flooding, microemulsion flooding, surfactant/polymer (SP) flooding and foam flooding for review. The sulfonated betaine surfactants have good temperature resistance and salt tolerance, low critical micelle concentration (cmc) and surface tension corresponding to critical micelle concentration (γ_cmc), good foaming properties and wettability, low absorption, ultralow interfacial tension of oil/water, and excellent compatibility with other surfactants and polymers. Sulfobetaine surfactants with ethoxyl structures, hydroxyl and unsaturated bonds, and Gemini sulfobetaine surfactants will become an important direction for tertiary oil recovery because they have better interfacial activity in high-temperature (≥90°C) and high-salinity (≥10⁴ mg/L) reservoirs. Some problems existing in the synthesis and practical application were also reviewed.     

Effects and measurements of polyoxyethylene block length in polyoxyethylene-polyoxybutylene copolymers

Block copolymer surfactants, made from 1,2-butylene oxide (BO), propylene oxide (PO) and ethylene oxide (EO), exhibit wide ranges of properties and performance. In particular, BO/EO block copolymers exhibit improved surfactant performance with respect to PO/EO analogs. One interesting difference between these two classes of surfactants is the EO capping efficiency of polyoxypropylene (POP) vs. polyoxybutylene (POB) hydrophobe secondary hydroxyl groups. In this regard, nuclear magnetic resonance measurements have shown that POP secondary diols react more readily with EO than POB diols. For the case of ethoxylated POB polymers, the amount of unethoxylated secondary hydroxyl is proportional to the average length of the polyoxyethylene (POE) blocks. Differential scanning calorimetry was used to observe crystallinity of POE blocks. For a given POB hydrophobe molecular weight and weight percentage EO, surfactant performance properties can be augmented by affecting POE block length in the ethoxylation process.     

Interfacial Tensions of Ethoxylated Fatty Acid Methyl Ester Solutions Against Crude Oil

The dynamic interfacial tension (IFT) of ethoxylated fatty acid methyl ester solutions against n‐alkanes, kerosene, and diluted heavy oil have been investigated by spinning drop interfacial tensiometry. The influences of ethylene oxide (EO) groups and alkyl chain length on IFT were investigated. The experiment results show that the water solubility decreases with an increase in alkyl chain length or a decrease in EO groups. The ability to lower the interfacial tension against hydrocarbons improves with both increasing alkyl chain length and EO group at the best hydrophilic‐lipophilic balance, which can be attributed to the enhancement of the interfacial hydrophobic interactions and the rearrangement of interfacial surfactant molecules. The mixed adsorption of surfactant molecules and surface‐active components may reduce IFT to a lower value. C₁₈=E₃ shows the best synergism with surface‐active components. However, the IFT values against pure crude oil are obviously higher than those against hydrocarbons, which may be caused by the nature of heavy oil.     

A New Series of Double-Chain Single-Head Sulfobetaine Surfactants Derived from 1,3-Dialkyl Glyceryl Ether for Reducing Crude Oil/Water Interfacial Tension

A new series of sulfobetaine surfactants with double-chain single-head structure were derived from 1,3-dialkyl glyceryl ethers and their performances in reducing Daqing crude oil/connate water interfacial tension (IFT) in the absence of alkali were studied. With a large hydrophilic head group and double hydrophobic chains, these surfactants are efficient at reducing crude oil/connate water IFT. Those with didecyl and dioctyl are good hydrophobic surfactants that can reduce Daqing crude oil/connate water to ultra-low IFT by mixing with a small molar fraction of various conventional single-chain hydrophilic surfactants, such as α-olefin sulfonates, dodecyl polyoxyethylene (10) ether, and cetyl dimethyl hydroxypropyl sulfobetaine. The asymmetric double-chain sulfobetaine derived from 1-decyl-3-hexyl glyceryl ether can reduce Daqing crude oil/connate water IFT to ultra-low solely over a wide concentration range (0.03–10 mM or 0.0017–0.58 wt.%), which allows for use of an individual surfactant instead of mixed surfactants to avoid chromatographic separation in the reservoir. In addition, formulations rich in sulfobetaine surfactants show low adsorption on sandstone, keeping the negatively charged solid surface water-wet, and forming crude oil-in-water emulsions. These new sulfobetaine surfactants are, therefore, good candidates for surfactant-polymer flooding free of alkali.     

一种高效浓缩洗衣液的研制

初步研究了脂肪醇聚氧乙烯醚硫酸钠(AES)、醇醚羧酸盐(AEC_9)、改性油脂、烷基糖苷(APG)及异构醇聚氧乙烯醚等5种表面活性剂在浓缩洗衣液中的应用,通过对去污力、泡沫性能、水溶分散性和酶活稳定性等的测试,将此几种表面活性剂与其他助剂复配,得到一种低泡、高效浓缩洗衣液。测试结果表明,自制浓缩洗衣液稳定,去污力强、可达到4倍浓缩的效果,水溶分散性好,无凝胶出现,酶活稳定性达87.1%。     

Contrasts in the surface activity of polyoxypropylene and polyoxybutylene-based block copolymer surfactants

Previous studies have shown that polyoxybutylene surfactant hydrophobes are less polar than polyoxypropylene hydrophobes. Polyoxyalkylene hydrophobes can be modified by ethoxylation to give terminal polyoxyethylene block hydrophilic groups. Polyoxybutylene/polyoxyethylene copolymer surfactants exhibit differentiated interfacial tensions, and wetting and foaming properties when compared to structurally equivalent polyoxypropylene/polyoxyethylene copolymers. There have been no reported comparisons, however, of polyoxybutylene/polyoxyethylene copolymers and polyoxypropylene/polyoxyethylene analogues in terms of fundamental parameters, such as critical micelle concentration, area per molecule at the interface, efficiency, and effectiveness. In one phase of this work, four polyoxybutylene/polyoxyethylene block copolymer surfactants were compared to structurally analogous polyoxypropylene/polyoxyethylene materials. Findings showed that polyoxybutylene/polyoxyethylene copolymers exhibited enhanced cotton wetting and lower surface and interfacial tensions compared to polyoxypropylene/polyoxyethylene analogues. Polyoxybutylene-based surfactants were typically one order of magnitude better in their ability to reduce surface tension at interface saturation. Polyoxybutylene/polyoxyethylene copolymers pack more efficiently at the interface, as evidenced by a smaller area per molecule at the interface. Critical micelle concentration values were also lower for polyoxybutylene/polyoxyethylene copolymers. A second phase of experiments focused on the surface activity of polyoxypropylene/polyoxyethylene triblock copolymers with higher molecular weight hydrophobes. Enhanced surface activity was found when compared to lower-molecular weight polyoxypropylene/polyoxyethylene copolymers.     

脂肪醇聚氧乙烯-3-醚琥珀酸单酯磺酸盐泡沫性能研究

用罗氏法对脂肪醇聚氧乙烯 3 醚琥珀酸单酯磺酸钠(AESM 3)表面活性剂的泡沫性能进行了系统研究,测定了其在不同浓度、不同温度、不同硬度水中的泡沫性能,并与两种同类表面活性剂的泡沫性能进行了对比。结果表明,AESM 3是一种起泡性与稳泡性皆优的高泡性表面活性剂品种。     

Thermal stability of nonionic polyoxyalkylene surfactants

Nonionic surfactants are largely employed in the pharmaceutical, cosmetic, and textile industry. The sensitivity of polyoxyethylene chains to autoxidation is studied because it is responsible for unpleasant effects such as discoloration, degradation of products, and unpleasant odors. In the present work, thermal stability of polyoxyethylene and polyoxyethylene/propylene nonionic surfactants has been studied by employing together differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). First of all, the thermal stability of three monodispersed surfactants (laurilic alcohol plus 4, 6, or 8 EO units) has been studied. Then, the behavior of these products has been compared with those of commercial surfactants containing the same alkyl chain coupled with idrophylic chains of different lengths, containing EO units alone or both EO and PO. The effect of the alkyl chains has also been examined in the same way. In all cases, autoxidation starts at about 100°C with a net heat production proportional to the number of adducts and equal to about (1.5–1.7) × 10⁵ J/adduct. Heat evolution stopped at about the same temperature, independently of the hydrophylic chain length. A residual of 10–30% by weight decomposes, at higher temperatures, with a very small heat evolution. The interpretation of these and other phenomena observed conclude the paper.     

羧酸盐Gemini表面活性剂合成及性能

以脂肪醇聚氧乙烯醚为原料,合成了羧酸盐阴-非Gemini表面活性剂,针对胜利油田某区块的油水,进行了表面活性剂的耐温抗盐性能、聚表配伍性能试验。结果表明,其耐盐可达50000mg/L、抗钙镁离子达到1000mg/L、耐温性能达90℃,聚表配伍性能良好,具有应用于三次采油(EOR)先导试验的前景。     

Preparation and Performance Evaluation of Fatty Amine Polyoxyethylene Ether Diethyl Disulfonate for Enhanced Oil Recovery in High‐Temperature and High‐Salinity Reservoirs

To enhance oil recovery in high‐temperature and high‐salinity reservoirs, a novel fatty amine polyoxyethylene ether diethyl disulfonate (FPDD) surfactant with excellent interfacial properties was synthesized. The interfacial tension (IFT) and contact angle at high temperature and high salinity were systematically investigated using an interface tension meter and a contact angle meter. According to the experimental results, the IFT between crude oil and high‐salinity brine water could reach an ultra‐low value of 10^?3 mN m^?1 without the aid of extra alkali at 90°C after aging. The FPDD surfactant has strong wettability alternation ability that shifts wettability from oil‐wet to water‐wet. The FPDD surfactant with a high concentration also has good emulsion ability under high‐temperature and high‐salinity conditions. Through this research work, we expect to fill the lack of surfactants for high‐temperature and high‐salinity reservoirs and broaden its great potential application area in enhanced oil recovery.     

Synthesis and surface activity of nonionic surfactants containing fluorocarbon hydrophobes

Nonionic surfactants having polydisperse polyoxyethylene chains and highly fluorinated hydrophobes were synthesized via a complex reaction route and their adsorption at water/air interfaces studied. They exhibit high surface activity and decrease both effectively and efficiently the surface tension of their aqueous solutions. The effect of the length of the polyoxyethylene chain upon surfactant surface activity is relatively low. Lower values of surface tension, below 30 mN m^?1, are obtained for surfactants having a low degree of ethoxylation. Surfactants having two terminal highly fluorinated hydrophobes are less surface active than analogues with one terminal hydrophobe.     

Optimization of Dynamic Interfacial Tension for Crude Oil–Brine System in the Presence of Nonionic Surfactants

In this study, interfacial tension (IFT) is measured between brine and crude oil (a sample of heavy oil from an Iranian oil reservoir) in the presence of two nonionic surfactants, KEPS 80 (Tween 80) and Behamid D, at different concentrations in order to optimize the concentrations of the surfactants. The surface response method is used to design the IFT measurement experiments. The experimental design and optimization is performed using the IFT as an objective function and temperature, concentration, and time as independent variables. In addition to the IFT measurement, various experiments such as stability tests of the surfactants in NaCl brine solutions, adsorption experiments on the carbonated rock surface, and phase behavior tests are performed to investigate the behavior of KEPS 80 and Behamid D in the enhanced oil recovery process. At the end, a model using the response surface statistical technique is designed for optimization of the concentrations of the surfactants, and a surfactant molecular migration mechanism is used for explanation of the dynamic IFT variation versus time. In the case of IFT experiments, the effect of surfactant concentration (at 1000, 3000, and 5000 ppm) on the dynamic IFT is investigated. The experiments are performed at four temperatures (25, 40, 50, and 67°C). The results show that the oil–brine IFT values can be reduced to about 4 mN m⁻¹ in the presence of Behamid D and to about 1 mN m⁻¹ in the presence of KEPS 80 at low concentrations.     

乙氧基化催化剂的研究进展

聚氧乙烯型非离子表面活性剂在表面活性剂行业及精细化工领域占有重要地位,其主要来源是乙氧基化产物。乙氧基化催化剂的研究进展将是推动非离子表面活性剂行业技术进步的重要因素。结合近年来国内外相关的研究工作,综述了乙氧基化催化剂的研究进展,对各类催化剂的催化性能和机理进行了分析,为以后乙氧基化催化剂的研究方向提出了建议。     

A Zwitterionic Surfactant Bearing Unsaturated Tail for Enhanced Oil Recovery in High‐Temperature High‐Salinity Reservoirs

High‐temperature/high‐salinity (HTHS) reservoirs contain a significant fraction of the world's remaining oil in place and are potential candidates for enhanced oil recovery (EOR). Selection of suitable surfactants for such reservoirs is a challenging task. In this work, two synthesized zwitterionic surfactants bearing a saturated and an unsaturated tail, namely 3‐(N‐stearamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate and 3‐(N‐oleamidopropyl‐N,N‐dimethyl ammonium) propanesulfonate, respectively, were evaluated. The surfactant with the unsaturated tail showed excellent solubility in synthetic seawater (57,643 ppm) and in formation brine (213,734 ppm). However, the unsaturated surfactant with a saturated tail showed poor solubility, and therefore it was not evaluated further. The thermal stability of the synthesized unsaturated surfactant solution in seawater was evaluated by heating the solution at 90 °C in a sealed aging tube for 2 weeks. The thermal stability of the unsaturated surfactant was confirmed by FTIR and NMR analysis of the aged samples at such harsh conditions. The critical micelle concentration (CMC) of the synthesized unsaturated surfactant in seawater was 1.02 × 10^?4 mol L^?1, while the surface tension at CMC was 30 mN m^?1. The synthesized unsaturated surfactant was able to reduce the oil–water interfacial tension to ~10^?1 mN m^?1 at different conditions. A commercial copolymer of acrylamide and 2‐acrylamido‐2‐methylpropane sulfonic acid (AM‐AMPS) was tested for EOR applications in HTHS conditions. The addition of the synthesized unsaturated surfactant to the AM‐AMPS copolymer increased the viscosity of the system. The increase in oil recovery by injecting the unsaturated surfactant solution and the surfactant–polymer mixture in solution was 8 and 21%, respectively. The excellent properties of the synthesized unsaturated surfactant show that surfactants with an unsaturated tail can be an excellent choice for HTHS reservoirs.     

4种阴离子表面活性剂易漂洗性能的比较研究

采用实验室建立的同时测定模拟漂洗硬水条件下泡沫衰减性和织物上表面活性剂的初始/残留吸附量的方法,对家居织物洗涤剂中常用的4种典型的阴离子表面活性剂的易漂洗性能进行了比较研究,并考察了易漂洗性能与表面活性剂的钙离子稳定性之间的关系。实验结果表明,表面活性剂的钙离子稳定性与硬水漂洗液的泡沫性正相关,而与表面活性剂在织物上的初始/残留吸附量负相关。具有适中钙离子稳定性的改性羧酸盐(N-月桂酰基肌氨酸钠)具有最佳易漂洗性,磺酸盐(十二烷基苯磺酸钠)次之,而钙离子稳定性极低的皂类(月桂酸钠)或钙离子稳定性极高的阴-非离子型硫酸酯盐(十二烷基聚氧乙烯醚硫酸钠)均不属于易漂洗表面活性剂。这一研究结果对易漂洗阴离子表面活性剂的分子结构设计以及节水型洗涤剂的研发具有理论指导意义和应用价值。     

驱油用脂肪醇聚氧乙烯醚磺酸盐研究进展

介绍了卤化脂肪醇醚法、烯烃加成法、硫酸酯盐转化法和羟乙基磺酸钠法合成脂肪醇聚氧乙烯醚磺酸盐的路线、工艺特点及优缺点,剖析了其泡沫性能的影响因素,耐温、耐盐耐钙性能的研究现状。脂肪醇聚氧乙烯醚磺酸盐类阴-非离子表面活性剂适用于高温、高矿化度油藏条件的开采,具有常规表面活性剂的多种优良性能,在油田开采中具有广阔的发展空间。     

醇醚羧酸盐物化性能的研究

对淡同环氧乙烷（简称ＥＯ）加合数的醇醚羧酸及其盐（简称ＡＥＣ）的表面张力、临界胶束浓度、泡沫性能、复配性能、温和性能等物化性能进行的检测评价表明：非离子醇醚经羧甲基化后发泡能力大大提高;ＥＯ加合数较高的ＡＥＣ具有更佳的去污能力和温和性,弱酸性介质对高ＥＯ加合数的ＡＥＣ提高云污效果有利。ＡＥＣ对皮肤和粘膜无刺激,能与包括阳离子活性剂在内的各类活性组份复配。不同羧甲基化度和ＥＯ加合数的ＡＥＣ产品在性能