碱对重烷基苯磺酸盐和无酸油相间界面张力的影响

以不含酸性物质的脱酸直馏柴油作为油相,研究了NaOH对重烷基苯磺酸盐/油体系界面张力的影响.结果表明,NaOH与原油中的石油酸反应生成自表面活性剂并不是油/水界面张力降低的主控因素.NaOH可以改变重烷基苯磺酸盐体系的最小烷烃碳数,从而影响界面张力,使界面张力达到超值.     

两种石油磺酸盐与不同原油间界面张力的探讨

考察了不同体系与不同原油间的界面张力变化.主要讨论了Na2CO3质量浓度、体系组成和原油种类对界面张力的影响.结果表明:单独使用石油磺酸盐的体系降低界面张力的能力较低,且达到超低界面张力的Na2SCO3质量浓度范围较窄.1#石油磺酸盐/异丙醇/磺酸盐表面活性剂DS复配体系(F3)降低大庆原油界面张力的能力最优,且达到超低界面张力的碱范围较宽.2#石油磺酸盐复配前后与大庆原油、大港原油间界面张力的变化不太显著,界面张力在10-3mN/m-1～10-2mN/m-1.     

Effects of oil phase viscosity on interfacial tension behaviour of oil/alkaline systems as measured by the spinning drop tensiometer

This note examines the effects of oil phase viscosity on the interfacial tension of reacting systems (acidic crude oils in contact with alkaline solutions) as measured by the Spinning Drop Tensiometer. Surfactants are produced by chemical reactions at the interface, thereby causing the shape of the oil droplet in the tensiometer to change continuously. The rates of droplet elongation/contraction are necessarily influenced by the oil phase viscosity, thereby affecting directly the measured interfacial tension. The principal conclusion of this work is that although oil phase viscosity exerts a significant effect on the dynamic interfacial tension after attainment of the minimum value, it makes for only a small absolute change in the magnitude of the minimum interfacial tension itself.     

超低界面张力重烷基苯磺酸盐复配驱油剂研究

研究了不同浓度的重烷基苯磺酸盐对长庆油田S区块的原油界面张力的影响,将重烷基苯磺酸盐与阴离子和甜菜碱表面活性剂复配,使油/水界面张力降至超低(10^(-3) mN/m数量级),并研究复配体系的乳化、自发乳化、耐温耐盐以及稳定性。结果表明,重烷基苯磺酸盐的复配体系具有优秀的降低界面张力的能力,尤其是与石油磺酸盐和椰油酰胺丙基羟基磺基甜菜碱(CHSB),能够大幅提升界面张力性能,同时两种复配体系具有优异的耐温耐盐稳定性。     

石油磺酸盐及其与脂肪醇醚磺酸盐复配体系的耐盐性能和界面性能

通过对胜利馏分油的磺化制得一种石油磺酸盐(PS),并对其与不同碳链脂肪醇醚磺酸盐(AnESO,EO=3,n=1214,16,18)复配体系的耐盐(NaCl、CaCl2)性能和界面性能进行了研究。结果表明:(1)PS耐盐性能较差,当NaCl质量浓度达到30 g/L或CaCl2质量浓度达到0.15 g/L时,即有沉淀生成,且与胜利原油间的界面张力值较高(≥10-1 mN/m)。(2)将PS和AnESO以m(PS)∶m(AnESO)=9∶1复配,复配体系的耐盐性能均明显提高。其中PS/A18ESO复配性能最好,复配体系NaCl质量浓度能达到80 g/L,CaCl2质量浓度则达到2.4 g/L;而且界面张力在一定NaCl和CaCl2含量下可以降至10-2 mN/m数量级。     

双烷基苯磺酸钠的合成及张力性能研究

分3步合成了双烷基苯磺酸钠:分子筛MCM-22催化α-烯烃与烷基苯合成双烷基苯磺酸;双烷基苯与氯磺酸反应生成双烷基苯磺酸;双烷基苯磺酸与NaOH中和反应生成双烷基苯磺酸钠。得到了最佳反应体系物质的量比n(烷基苯)∶n(α-烯烃)=4∶1,磺化反应条件30℃,60 min。并对合成的双烷基苯磺酸钠C12-6、C12-10、C12-14进行张力性能测试,分析了这3种不同链长双尾形表面活性剂的起泡力和稳泡力、乳化性能、润湿性能、临界胶束浓度以及弱碱条件下油水界面张力性能差异。     

超低界面张力石油磺酸盐复配驱油剂研究

通过室内实验研究了溶液质量分数、矿化度对石油磺酸盐溶液与大庆L区块原油的界面张力的影响,并将不同类型表面活性剂分别与石油磺酸盐复配,筛选出能够使油/水界面张力降至超低(10-3 mN/m数量级)的最优增效组合,以取代ASP复合驱中所加的碱.实验结果表明,在矿化度为6 000～10 000 mg/L,钙、镁离子质量浓度不超过20 mg/L时,石油磺酸盐表面活性剂有良好的抗盐性,可使油/水界面张力达到超低.在实验所选的不同类型表面活性剂中,石油磺酸盐与甜菜碱型表面活性剂复配起到明显的增效作用,特别是与椰油酰丙基磺基甜菜碱复配增效作用尤为显著,且两者复配的浓度范围较宽,油/水界面张力易达到超低.     

重烷基苯磺酸盐复配体系获得超低油水界面张力

将阴离子表面活性剂窄馏分重烷基苯磺酸盐(HABS 3#)与不同类型的表面活性剂复配,并测定复配体系对十二烷/水溶液的界面张力。结果表明,阴离子HABS 3#与非离子脂肪醇聚氧乙烯醚(AEO-9)、两性离子椰油酰胺甜菜碱(CAB-35)、阴离子窄馏分重烷基苯磺酸盐(HABS 1#)复配后,均能在总浓度为0.01%时,在一定的复配比例下,使得油水界面张力降至超低(10^(-3)mN/m),而与阳离子十六烷基三甲基溴化铵(CTAB)复配后,体系对油水界面张力反而升高。获得最低油水界面张力时的复配比例分别为AEO-9含量15%,CAB-35含量40%,HABS 1#含量10%,CTAB含量0。     

重烷基苯磺酸盐复配体系获得超低油水界面张力

将阴离子表面活性剂窄馏分重烷基苯磺酸盐(HABS 3#)与不同类型的表面活性剂复配,并测定复配体系对十二烷/水溶液的界面张力。结果表明,阴离子HABS 3#与非离子脂肪醇聚氧乙烯醚(AEO-9)、两性离子椰油酰胺甜菜碱(CAB-35)、阴离子窄馏分重烷基苯磺酸盐(HABS 1#)复配后,均能在总浓度为0.01%时,在一定的复配比例下,使得油水界面张力降至超低(10~(-3)mN/m),而与阳离子十六烷基三甲基溴化铵(CTAB)复配后,体系对油水界面张力反而升高。获得最低油水界面张力时的复配比例分别为AEO-9含量15%,CAB-35含量40%,HABS 1#含量10%,CTAB含量0。     

Factors affecting oil/water interfacial tension in detergent systems: Nonionic surfactants and nonpolar oils

Because earlier model detergency studies have shown that oil/water interfacial tension is critically important in oil removal processes, factors affecting the interfacial tension between detergent-range nonionic surfactant solutions and paraffin oil have been examined. For a given hydrophobe, equilibrium interfacial tension values increase with the length of the ethylene oxide chain in the hydrophile, because of the attendant decrease in overall surface activity. For a given degree of ethoxylation, commercial nonlphenol ethoxylates reduce interfacial tension more effectively than their secondary alcohol-based counterparts, and these in turn are more effective than commercial primary alcohol ethoxylates. Furthermore, monodisperse primary alcohol ethoxylates reduce interfacial tension more effectively than broad-range ethoxylates with similar cloud points. This observed order of effectiveness is attributed in part to variations in the extent of fractionation that occur as nonionic surfactants divide between the oil and water phases. Equilibrium interfacial tension values produced by commercial nonionic surfactants are significantly more dependent on concentration and temperature than those obtained with monodisperse ethoxylates. However, the time-course for lowering interfacial tension exhibited by monodisperse ethoxylates varies with concentration and temperature to a greater extent than that displayed by commercial products. These findings are accounted for by the combined effects of the changes in relative surface activity and partitioning that occur as the concentration and temperature are varied. An imidazoline-based quaternary fabric softener markedly increases the interfacial tension immediately following phase contact, whereas equilibrium values are only slightly higher in the presence of the softener. Appatently, preferential adsorption of the softener occurs at the interface, followed by adsorption of the nonionic surfactant at the new softener/water interface. Builders and electrolytes have no significant effect on the interfacial tension between aqueous nonionic surfactant solutions and paraffin oil. Terg-O-Tometer results demonstrate the correlation between oil/water interfacial tension and detergency.     

居贝特甜菜碱对克拉玛依原油的动态界面张力行为

考察了5种含聚氧乙烯链的居贝特甜菜碱溶液与克拉玛依原油在40℃下的动态界面张力与质量分数间的关系。结果表明,对于质量分数为0.01%～0.2%的GC16(3),GC16(5)和GC16(7)体系及GC20(5)和GC20(9)体系,当碳链长度相同时,随着聚氧乙烯链的增长,界面张力逐渐升高;当聚氧乙烯数相同时,随着碳链长度的增加,界面张力降低。     

芳基烷基磺酸盐链长对烷烃的油-水动态界面张力的影响

采用旋转滴法测定系列自制芳基烷基磺酸盐（C_nNPAS, n=8,10,12,14,16）水溶液对烷烃的油-水动态界面张力,考察了表面活性剂烷基链长、表面活性剂浓度、弱碱浓度、烷烃碳数等因素对油-水动态界面张力的影响。结果表明,增大C_nNPAS的烷基链长和碱含量均会使界面张力达到稳定值的时间增长;增加C_nNPAS浓度和烷烃碳数均会使界面张力动态变化加快,达到平衡所需时间减少。C_nNPAS表面活性剂可在低浓度范围较明显地降低界面张力,而随着浓度的增加界面张力回升明显。     

Use of mixed surfactants to improve the transient interfacial tension behaviour of heavy oil/alkaline systems

The objective of this study was to identify suitable combinations of additives to aqueous alkaline formulations for the potential recovery of Saskatchewan heavy crude oil. A previously developed strategy was applied to screen various additive combinations consisting of three commercial petroleum sulfonate surfactants and two commercial lignosulfonate surfactants. The selection of the additives was based on a large number of physical and interfacial property measurements in conjunction with phase stability tests at different temperatures. The resulting ternary formulations, labelled here as Mixed-Surfactant-Enhanced Alkaline (MSEA) systems, were very successful in reversing the trend of increasing interfacial tension with time that characterizes additive-free alkaline/crude oil systems. This success came at the expense of initial IFT values that were considerably higher than those exhibited by the corresponding additive-free alkaline solutions. However, at higher temperatures (65 °C), these ternary MSEA formulations were capable of generating very low IFT values against the crude oil (in the range of 5 × 10^?2 to 10^?1 mN/m), which suggests that they could be suitable candidates for commercial exploitation of heavy oil recovery processes.     

Effects of water-soluble polymers and aqueous-phase viscosity on the interfacial tension behavior of reacting oil–alkaline systems

This study presents the results of an experimental study of the effects of water-soluble polymer additives on the dynamic interfacial tension behavior of reacting oil–aqueous systems as measured by the spinning drop tensiometer. Polymer additives can exert both a direct physico-chemical effect and an indirect viscosity effect on the measured interfacial tension. This work, which complements an earlier study dealing with the effects of oil-soluble polymer additives, reveals that the nominal effects of aqueous-phase viscosity are opposite to those of oil-phase viscosity. In particular, an increase in aqueous-phase viscosity produces an increase in the rate of increase of the apparent interfacial tension after attainment of the minimum value. These differences are explained in terms of the dependence of diffusion rates and interfacial adsorption on aqueous-phase viscosity. The conclusion of principal practical interest is that although aqueous-phase viscosity exerts only a small effect on the dynamic interfacial tension at small times (i.e., prior to attainment of the minimum value) it exerts a very significant effect thereafter. © 1994 John Wiley & Sons, Inc.     

Dynamic interfacial tension minima in finite systems

A physical model is presented to explain the dramatic interfacial tension minima that may sometimes occur during the equilibration of a surface-active solute between two liquid phases. The effects of bulk phase mass transfer resistances, interfacial sorption kinetics, and finite phase volumes are included. Adsorption and desorption barriers are treated both by linear and Langmuir kinetics. Dynamic interfacial tension minima are predicted whenever the solute mass transfer resistance is higher and/or a large desorption barrier exists in the phase towards which transfer is occurring. Experimental dynamic tension minima for acidic organic phases contacting an alkaline aqueous phase can be rationalized by the existence of desorption barriers. The relevance of such tension minima to interfacial turbulence, spontaneous emulsification, and enhanced oil recovery is discussed.     

脱蜡油磺酸盐合成工艺及界面活性研究

通过溶剂萃取的方法,利用N-甲基吡咯烷酮将减二线脱蜡油切割成极性不同的8个族组分,以第1族组分为原料,氯磺酸为磺化剂合成石油磺酸盐。研究反应条件对产品收率的影响,并且测定其界面张力。实验结果表明:以收率为指标,第1族组分石油磺酸盐最佳合成工艺为反应温度60℃、酸油比0.36、反应时间60min、老化时间20min;第1族组分石油磺酸盐界面活性较差。     

Effects of temperature and time on interfacial tension behavior between heavy oils and alkaline solutions

Heavy oils contain significantly more acidic components than conventional crude oils. Upon contact with aqueous alkaline solutions, water-soluble surfactants are formed in-situ at the interface. These surfactants have the ability to reduce the oil/water interfacial tension to ultra-low values. This work studies the significant effects of time and temperature on the interfacial tension between alkaline solutions and two Canadian heavy oils (Lloydminster and Cold Lake). The results obtained indicate that the time period during which interfacial tension remains ultra-low is just as important as the magnitude of the minimum attainable interfacial tension in determining the potential success of an alkaline flooding process in the field.     

复合体系与原油多次乳化过程中油水界面张力变化规律

为进一步了解三元复合驱驱油机理,深入研究复合驱油过程中原油与复合体系两相流体在地层中多次接触乳化过程中界面张力变化规律,在地层温度45℃条件下,开展了一系列不同含水率下强碱三元复合体系与大庆原油多次乳化实验。结果表明,复合体系与原油多次接触乳化后,具有较强地保持超低界面张力的能力;水相分别与上相油和原油间界面张力能够达到超低的乳化次数随含水增加而增加;乳化次数相同时,水相与原油间界面张力低于其与上相油间界面张力;随着乳化次数增加,三元体系与原油间最低界面张力值有先下降后升高的趋势;无论是与原油间界面张力还是与上相油间界面张力达到超低时的乳化次数二元体系都多于三元体系,说明复合驱注入段塞优化时可适当考虑二元体系。     

复合体系与原油多次乳化过程中油水界面张力变化规律

为进一步了解三元复合驱驱油机理,深入研究复合驱油过程中原油与复合体系两相流体在地层中多次接触乳化过程中界面张力变化规律,在地层温度45℃条件下,开展了一系列不同含水率下强碱三元复合体系与大庆原油多次乳化实验。结果表明,复合体系与原油多次接触乳化后,具有较强地保持超低界面张力的能力;水相分别与上相油和原油间界面张力能够达到超低的乳化次数随含水增加而增加;乳化次数相同时,水相与原油间界面张力低于其与上相油间界面张力;随着乳化次数增加,三元体系与原油间最低界面张力值有先下降后升高的趋势;无论是与原油间界面张力还是与上相油间界面张力达到超低时的乳化次数二元体系都多于三元体系,说明复合驱注入段塞优化时可适当考虑二元体系。     

石油磺酸盐及其复配体系的界面性能研究

通过对胜利馏分油的磺化制得一种石油磺酸盐(SHL-PS),并采用IR和ESMS对其结构和相对分子质量分布进行了表征,分别测定其表面性能和油水界面张力.结果显示,SHL-PS的相对分子质量分布集中在190～600,γcmc为32.04 mN·m-1,cmc为8.88 mg·L-1;与孤东原油的界面张力在低质量分数(0.1%-0.2%)下即可达到超低界面张力(<10-2mN·m-1);其最佳矿化度约为10 g/L,与胜利地层水基本相当;石油磺酸盐/C1416 α-烯基磺酸钠(SHL-PS/C1416AOS)和石油磺酸盐/十八醇聚氧乙烯醚磺酸钠(SHL-PS/C18E3SO)复配体系均可将界面张力降低到10-3mN·m-1数量级,但机理有所不同.