石油磺酸盐结构与界面活性关系研究

对25个不同来源及批次的石油磺酸盐样品进行界面张力测试、质谱分析,研究了其结构与界面活性之间的相互关系.实验结果表明:高碳链C17~C25磺酸盐含量的高低对界面活性具有最主要的影响,含量较高则界面活性较优.另外当样品所含组分的分子量在200~800范围内均匀分布时,相对丰度最大的分子离子峰聚集在479(C23苯磺酸盐)附近的样品界面活性则较优.     

Experimental Study of the Effect of Strong Alkali on Lowering the Interfacial Tension of Oil/Heavy Alkylbenzene Sulfonates System

Experimental studies were conducted to explore the fundamental mechanisms of alkali to lower the interfacial tension of oil/heavy alkylbenzene sulfonates (HABS) system. Sodium hydroxide was used as the strong alkali chemical to investigate the interfacial tension (IFT) of oil/HABS system. The influences of salt and alkali on the interfacial activity were studied by the measurement of interfacial tension and partition coefficient. Moreover, the alkali/surfactant solutions were measured by dynamic laser scattering. The results showed that compared with the salt, the function of alkali to lower the interfacial tension and improve partition coefficient is more significant. The micelles formed by surfactants could be disaggregated because of adding alkali, so the size of micelles decreases and the number of mono‐surfactants increases, then more surfactant molecules move to the interface of oil/surfactant system and the adsorption of surfactants at oil‐water interfaces increases, which can lead to the decrease of IFT.     

The Effects of Di- or Polysulfonates on Adsorption of Petroleum Sulfonates

Petroleum sulfonates was separated into several fractions with conventional extraction method according to the polarity of extraction solvent. The relative content of mono-, di-, or polysulfonates in each fraction was determined by using high pressure liquid chromatography and then the average sulfonic amount of each fraction can be calculated according to above results. The equivalent weight of each fraction was measured by both two-phase titration method and ESI-MS method, and the results shows the tow methods are comparatively coincident. Furthermore, the mean molecular weight of each fraction can be calculated with the average sulfonic amount and the equivalent weight. Adsorption isotherm and coreflooding adsorption test were both conducted to determine the adsorption amount and adsorption rate of each fraction. It was found that the fraction with the minimum equivalent weight is middle mean molecular weight and its adsorption amount on reservoir sand is maximal. Moreover, two fractions have a tendency to come to saturated adsorption in coreflooding adsorption test, but the time needed for saturated adsorption is distinctly different. However, the total adsorption amount of the other fractions keeps increasing at all time. The mechanisms accounting for the difference of adsorption performance were proposed on the basis of the diverse composition of the fraction.     

重烷基苯磺酸盐的界面性质和驱油机理

重烷基苯磺酸盐是在三次采油中广泛采用的表面活性剂之一，但重烷基苯原料组成复杂导致最终磺化产物的驱油效果差异很大.实验通过柱层析的方法将重烷基苯分离成6个族组分，并对其中的二烷基苯、单烷基苯和二烷基茚萘满、烷基萘、多苯烷进行磺化，中和提纯后对各磺酸盐进行界面张力测定.通过对比不同矿化度下界面张力以及各组分复配后的界面张力，对原油等效烷烃数(EACN)以及各组分碳数最低值(nmin)测定，得出各组分之间协同效应的规律和复配机理，从而阐明了重烷基苯磺酸盐的驱油机理.通过研究十二烷基苯磺酸钠(LAS)与各组分之间的复配作用对上述规律和机理进行了进一步验证.     

Effects of a Novel Organic Alkali on the Interfacial Tension and Emulsification Behaviors Between Crude Oil and Water

Experiments have been carried out to investigate the interfacial tension (IFT) and emulsification behaviors between Shengli crude oil and a novel organic alkali (OA). The dynamic IFT and minimum IFT are adopted to characterize the IFT behaviors; the microscopic method, Turbiscan stability index, separated water rate, and laser particle size analysis method are used to show the emulsification behaviors. The dynamic and minimum IFT both decrease continuously with the increase of OA concentration whether surfactant is added or not; because of the synergy of OA and surfactant, the minimum IFT will be reduced to the ultralow value. The synergy is also crucial for the crude oil emulsification. When OA and surfactant are used together, owing to the mosaic and cross-multiple adsorption of OA, surfactant and in situ soap at the interfacial film, the oil can be emulsified more easily, the quantity of emulsified droplets is higher, and the emulsion is more stable with OA concentration increases. The relationship of the minimum IFT and emulsification is investigated; it indicates that the emulsion stability improves, the degree of dispersed homogeneity of oil droplets increases, and the median diameter of emulsified oil droplets decreases with the decline of the minimum IFT.     

Study on the Mechanism of Asphaltenes Reducing Oil-Water Interfacial Tension

As high polar components of crude oil, asphaltenes play a significant role in reducing oil-water interfacial tension(IFT). In this paper, the effects of asphaltenes on reducing IFT in the presence of surfactant were compared, and the mechanism of asphaltenes reducing the IFT was studied by the dynamic interfacial tension(DIFT) equation. Whether asphaltenes were added to the oil or 2,5-dimethyl-4-(4-dodecyl) benzene sodium sulfonate(p-S14-4) was added to the water phase, either of all results in the IFT reducing and the IFT is related to the coverage and the mass of asphaltenes adsorption at the interface. In the presence of asphaltenes, the adsorption of the active substances to the interface is not entirely dependent on diffusion, and the process can be divided into three regions. Region I: the IFT rapidly reducing, this process is controlled by diffusion of surfactant; Region II: the IFT reducing slowly, resulted from the lower diffusion rate that is limited due to the aggregates formed by the interaction of asphaltene-asphaltene; Region III: the interaction of asphaltene-asphaltene is broken by the interaction of surfactant-asphaltene. The asphaltene aggregates are reduced and adsorbed rapidly at the interface. Furthermore, the results reveal that the asphaltenes concentration affects the coverage rate and adsorption at the interface.     

Foam Flooding with Ultra-Low Interfacial Tension to Enhance Heavy Oil Recovery

Severe viscous fingering during water flooding of heavy oil leaves a large amount of oil untouched in the reservoir. Improving sweep efficiency is vital for increasing heavy oil recovery. Previous researches have proved that foam flooding can increase the sweep efficiency and oil recovery. The polymers could make the foam more stable and have better plugging capacity, but the interfacial tension (IFT) of oil and water increase which could decrease the displacement efficiency of the heavy oil. In view of the deficiency of conventional foam flooding, it is necessary to research the ultra-low interfacial tension foam which could improve macro-swept volume and micro-displacement efficiency in heavy oil reservoir. In this paper a novel foam agent is developed by the combination of surfactant and additives to lower the IFT of oil and water. The operating parameters including foam injections modes and gas liquid ratio were investigated by core flooding experiments. Field test performance shows that oil production per day increased from 85.6 to 125.7 t, water cut declined from 92.1 to 83.6% after 3 months injection. This study provides a novel method to improve heavy oil recovery with an ultra-low interfacial tension foam flooding system.     

The Interfacial Tension and Alkane Carbon Number (nmin) of Alkyl Benzene Sulfonates in Relation to Enhanced Oil Recovery. Part I: Effect of Surfactant Molecular Weight/Temperature and Electrolyte on nmin

Twelve anionic monoisomeric surfactants based on the alkyl benzene sulfonic acid were prepared. In two sets of experiments, the (n_min) values were determined at 28 and 70°C for them. The n-hydrocarbon scans (n-C₅ to n-C₁₈) against the interfacial tension were used to determine the (n_min) values. The factors affecting (n_min) such as; molecular weight, branching of side chain, temperature and electrolyte addition were investigated. From the obtained results, it was found that the surfactants which has the highest molecular (8φ C₁₅ ABS) gave (n_min) equal 8, so it can be used in the enhanced oil recovery(EOR) without additives (the suitable (n_min) for EOR between 7-9). Otherwise, the lowest molecular weight surfactant (7φ C₁₃ ABS) gave (n_min) equal 5 without addition of alcohols or electrolyte. This case needs some additives to adjust the (n_min) in the range of 7 to 9. By investigation the factors affecting (n_min), it was found that the side chain of alkyl benzene shifted the (n_min) to the highest values. The increasing of temperature decreased the (n_min) values. Also, it was found that the (n_min) increased to high value by adding the electrolytes and alcohols. The mixture between surfactants with and without side chain shifted the (n_min) to the highest value. Using these parameters, the alkane carbon number (n_min) can be used to select the suitable solvent during the preparation of emulsion to get the minimum interfacial tension at which the maximum emulsion stability should be obtained and also to select the surfactant for EOR.     

Synthesis of Surfactants from Alkali Lignin for Enhanced Oil Recovery

With the cheap and abundant resource of alkali lignin as feedstock, surfactants for enhanced oil recovery were synthesized by amination and alkylation reaction of lignosulfonate. The effects of amination conditions, including the ratio of raw materials, amination reagent, temperature, and reaction time, on nitrogen contents and surface tension of the surfactants were investigated. The results showed that ethylenediamine was more suitable for amination, and the molar ratio of alkali lignin, ethylenediamine, and formaldehyde was 1:2:1.5 at 80°C for 5 hours. The structure of synthesized products was characterized by Fourier transform infrared spectrometry. The HLB value of synthesized product was 10. The interfacial tension between Daqing crude oil and synthetic water could be decreased to 10^?2 mN/m with synthesized surfactant and NaOH at 45°C. Moreover, the effects of molecular weight of surfactants on interfacial tension were also studied. The synthesized surfactant (M_w > 10,000) showed a better interfacial activity on Daqing crude oil.     

结构及助剂对十五烷基芳基磺酸盐吸附性能的影响

在45 ℃下,采用两相滴定法测定了4种自制高纯度十五烷基芳基磺酸盐在油砂上的吸附等温线。 分别考察了表面活性剂浓度、NaCl、NaOH、NaHCO3、正丁醇浓度及分子结构对表观吸附量的影响。 结果表明,随着磺酸盐浓度的增大,吸附量先增大后有所降低。 NaCl和NaOH的加入使吸附量增大,NaHCO3及正丁醇的加入使吸附量降低,且随着芳基位置向长烷基链中间的移动,吸附量降低,受助剂的影响变小。     

Ultra-Low Interfacial Tension Between Heavy Oil and Betaine-Type Amphoteric Surfactants

Betaine surfactants with lipophilic groups of different lengths were synthesized in this research and the dynamic interfacial tension (IFT) between solutions of these surfactants and three kinds of crude oil from Shengli Oilfield are measured. The results indicated that, for Gudao and Gudong heavy oil, cetyl dimethyl hydroxyl sulfobetaine (SBET-16) was the most efficient in lowering the IFT in the case of no alkalis, while for Shengtuo heavy oil, cetyl dimethyl carboxymethyl betaine (CBET-16) was best. SBET-16 with the concentration of 0.003–0.1% and 0.005–0.1% can reduce the oil/water IFT to ultra-low for Gudao and Gudong oil respectively, CBET-16 with the concentration of 0.005–0.1% can lower the oil/water IFT to ultra-low for Shengtuo oil. These results showed that for different oils, an oil displacement agent with high capacity to lower the oil/water interfacial tension may be obtained only by changing the molecular structure of betaine surfactant. This study can be used to guide the design of surfactants for alkaline-free combination flooding.     

Study on Foaming Properties and Dynamic Surface Tension of Sodium Branched-alkyl Benzene Sulfonates

Foaming properties and the dynamic surface tension (DST) were carried out with aqueous solutions of sodium branched-alkyl benzene sulfonates to elucidate the relationship between foaming properties and surfactant structures. The parameters of the DST (t*, n, R _1/2 ) are correlated with the foaming ability for alkyl benzene sulfonates with benzene ring substituting at positions 2, 4, and 8 of hexadecane. The parameters of the DST (t*, n, R _1/2 ) are correlated with the foaming ability of the same surfactant solutions. The results indicated that the molecular diffusion in the solution, adsorption, and arrangement at the air/water interface were changed with different molecular structures: changing the substituted position of benzene ring from 2 to 8 of hexadecane, the value of t* and n decrease, and the value of R _1/2 increases, which lead to the high dynamic surface activity and high foam volume. The foam stability is correlated with the high surface dilational elasticity and the strength of surface monolayer: changing the substituted position of benzene ring from 2 to 8 of hexadecane, the branched-alkyl chain becomes more flexible, which is characterized by densely packed adsorbed molecules and high film elasticity of the adsorption film. Therefore, the foam stability increases.     

由表面活性物质溶液的动界面张力外推求平衡界面张力的研究

表面活性物质溶液的界面张力往往随时间而变,难以测得平衡界面张力J。Kloubek^[1]曾应用经验式:1/(δ_H2O-δ_t)=b/(At^1/2)+1/A,以[1/(δ_H2O-δ_t)]对1/t^1/2作图外推求得溶液的平衡表面张力,但所得结果仅与文献值大致相符。本文从理论上分析该经验式的由来,以及产生偏离的原因,并寻求了解决的办法。     

阴阳离子表面活性剂混合体系在克拉玛依油田中获得超低界面张力

利用阴阳离子表面活性剂复配技术,在克拉玛依油田实际油水体系中获得了超低界面张力.通过添加非离子保护剂的第三组分,阴阳离子表面活性剂混合体系在克拉玛依油田回注水体系中的溶解度大大提高.确定了相关体系能够获得超低界面张力的表面活性剂的浓度和混合的比例范围,在克拉玛依油田的多个实际油水体系中获得了具有较大复配比例和较低表面活性剂浓度的实际配方,其中部分体系油水界面张力可接近10-4mN·m-1.同时,这类阴阳离子表面活性剂混合体系具有很好的抗吸附能力,在石英砂吸附72 h后体系依然呈现优良的超低界面张力.     

Synthesis of a New CO2 Philic Surfactant for Enhanced Oil Recovery Applications

The synthesis of CO₂ philic surfactant using maleic anhydride and 4-tert-butylbenzyl alcohol is reported. We reacted maleic anhydride with 4-tert-butylbenzyl alcohol to form bis(4-(tert-butyl)benzyl) fumarate and sulfonated the produced diester. The esterification reaction was optimized for a maximum yield of 98% of bis(4-(tert-butyl)benzyl) fumarate. First-order reaction kinetics with respect to acid was observed. The activation energy was found to be 55.62 kJ/mol. The sulfonated product of diester was obtained by the sulfonation reaction and the yield of 82% of surfactant was achieved. The in-house developed surfactant effectively lowered down the IFT between CO_2/brine to 4.2 mN/m. This surfactant is targeted for CO₂-EOR applications.     

电喷雾质谱法分析三次采油用石油磺酸盐

采用电喷雾质谱法测定了胜利油田三次采油用石油磺酸盐样品的分子量分布范围在200～600,数均分子量为488,重均分子量为534.鉴别出烷基苯磺酸盐、烷基萘磺酸盐、烷基茚满磺酸盐等为胜利油田磺酸盐的主要组分.同时对来自胜利、大庆、克拉玛依和玉门4个不同油田的石油磺酸盐进行区别分析.     

植物油酸／Tween－60复配体系与原油间的界面张力

研究了植物油酸及其中和物／Ｔｗｅｅｎ－６０复配体系与大庆原油间界面张力随各种因素的变化规律。结果表明，当０．４０％ＮａＣｌ存在时，植物油酸中和度为０．８５，ＮａＣｌ浓度为０．９０％时，复配以０．１０％Ｔｗｅｅｎ－６０既可使体系兼容，又可使之保持较低界面张力。     

油酸-油酸钠水溶液/原油间的瞬时界面张力

羧酸盐表面活性剂以其价格低廉、资源丰富和较高的界面活性而受到重视[1]．我们将廉价的天然核酸盐复配体系用于提高采收率研究，取得良好效果问．据最近报道问，用瞬时界面张力（l）评价驱油体系更符合实际采油过程．本文应用试剂级油酸，试图从理论上探讨不同因素对混合体系瞬时界面张力的影响规律，为驱油体系配方的选择提供依据．1实验部分1．1试剂油酸（R17C00H），分析纯收京长城化学试剂厂产品）．水解聚丙烯酸胶（HPAM），平均分子量为1．7X10’，平均水解度为20％，（美国辉瑞公司产品）．1．2方法按设计量在电子分析天平（精…     

植物油酸／Tween—60复配体系与原油间的界面张力

研究了植物油酸及其中和物／Ｔｗｅｅｎ－６０复配体系与大庆原油间界面张力随各种因素的变化规律，结果表明，当０．４０％ＮａＣｌ存在时，植物油酸中和度为０．８５，ＮａＣｌ浓度为０．９０％时，复配以０．１０％Ｔｗｅｅｎ－６０既可使体系兼容，又可使之保持较低界面张力。     

ASP复合驱油体系瞬时界面张力的研究

以胜利油田孤岛试验区原油为油相,用正交试验筛选了碱/天然混合羧酸盐/聚合物驱油体系,讨论了各组分对ASP复合驱油体系油水瞬时界面张力的影响,并探讨了各组分间的相互作用机理及其在油水界面的吸附机理。