石油磺酸盐对原油界面性质及其乳状液稳定性的影响

The influence of petroleum sulphonate （TRS） on interfacial properties and stability of the emulsions formed by formation water and asphaltene, resin and crude model oils from Gudong crude oil was investigated by measurement of interfacial shear viscosity, interfacial tension （IFT） and emulsion stability. With increasing petroleum sulphonate concentration, IFT between the formation water and the asphaltene, resin and crude model oils decreases significantly. The interfacial shear viscosity and emulsion stability of asphaltene and crude model oil system increase for the petroleum sulphonate concentration in the range 0.1% to 0.3%, and decrease slightly when the concentration of the surfactant is 0.5%. There exists a close correlation between the interfacial shear viscosity and the stability of the emulsions formed by asphaltene or crude model oils and petroleum sulphonate solution. The stability of the emulsions is determined by the strength of the interfacial film formed of petroleum sulphonate molecules and the natural interfacial active components in the asphaltene fraction and the crude oil. The asphaltene in the crude oil plays a major role in determining the interfacial properties and the stability of the emulsions.     

Experimental and modeling investigation of dynamic interfacial tension of asphaltenic-acidic crude oil/aqueous phase containing different ions

In this way,after experimental measurement of interfacial tension,different models including mono-exponential decay,dynamic adsorption models and empirical equation are used to correlate this time-dependent behavior of interfacial tension(IFT).During the modeling approach,the induction,adsorption,equilibrium,and meso-equilibrium times as well as diffusivity of surface active components known as natural surfactant including asphaltene and resin from crude oil to the interface are obtained.In addition,the surface excess concentration of surface active components at the interface and Gibbs adsorption isotherm are utilized to analyze the measured dynamic IFTs.Finally,the mechanisms of crude oil/aqueous solution IFT including(a)the activity of surface-active components and(b)surface excess concentration of them at fluid/fluid interface are proposed and discussed in details.     

超重力技术应用于不同磺化剂合成石油磺酸盐表面活性剂

With the application of HIGEE process intensification technology, petroleum sulfonate surfactant used for enhanced oil recovery was synthesized from petroleum fraction of Shengli crude oil with three sulfonating agents, including diluted liquid sulfur trioxide, diluted gaseous sulfur trioxide and fuming sulfuric acid. For each sulfonating agent, different operation modes (liquid-liquid or gas-liquid reaction with semi-continuous or continuous operation) were applied. The effects of various experimental conditions, such as solvent/oil mass ratio, sulfonating agent/oil mass ratio, gas/liquid ratio, gas concentration, reaction temperature, rotating speed, circulation ratio, reaction time and aging time, on the content of active matter and unsulfonated oil were investigated. Under relatively optimal reaction conditions, the target product was prepared with high mass content of active matter (up to 45.3%) and extremely low oil/water interfacial tension (4.5×10–3 mN•m–1). The product quality and process efficiency are higher compared with traditional sulfonation technology.     

Review on application of nanoparticles for EOR purposes: A critical review of the opportunities and challenges

Nanoparticles have already gained attentions for their countless potential applications in enhanced oil recovery.Nano-sized particles would help to recover trapped oil by several mechanisms including interfacial tension reduction, impulsive emulsion formation and wettability alteration of porous media. The presence of dispersed nanoparticles in injected fluids would enhance the recovery process through their movement towards oil–water interface. This would cause the interfacial tension to be reduced. In this research, the effects of different types of nanoparticles and different nanoparticle concentrations on EOR processes were investigated. Different flooding experiments were investigated to reveal enhancing oil recovery mechanisms. The results showed that nanoparticles have the ability to reduce the IFT as well as contact angle, making the solid surface to more water wet. As nanoparticle concentration increases more trapped oil was produced mainly due to wettability alteration to water wet and IFT reduction. However, pore blockage was also observed due to adsorption of nanoparticles, a phenomenon which caused the injection pressure to increase. Nonetheless, such higher injection pressure could displace some trapped oil in the small pore channels out of the model. The investigated results gave a clear indication that the EOR potential of nanoparticle fluid is significant.     

偶联阳离子表面活性剂和常用阴离子表面活性剂混合溶液的相分离和微观结构

The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-l,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.     

用198Au示踪法研究季铵盐体系萃取金

The solvent extraction of KAu(CN)2 from alkaline solution by quaternary ammonium salts (trialkylmethylammonium chloride or cetyltrimethylammonium bromide) waw investigated by means of ^198Au radioactive tracer method. Various parameters,such as the gold (I) concentration in aqueous phase,the modiffer,emulsifiation at the interface of two phases, and phase ratio used in the extraction of gold (I) were studied. The results demonstrate that almost all gold (I) in the aqueous phase was practically extracted into the organic phase. The water content in the organic phase decreased significantly with increase of gold (I) concentration using long chain alcohol as modifier,in contrast with the system with tributyl phosphate (TBP) as modifier. Emulsification at the interface of two phases decreases with an increase of modifier concentration in the organic phase or with the addition of a small amount of lysozyme into the aqueous phase. The method with ^198Au tracer can be directly used to determine the Au(I) concentration both in aqueous and organic phases, which is especially suitable for the low concentration of Au(I).     

Prediction of mass transfer coefficients in an asymmetric rotating disk contactor using effective diffusivity

Mass transfer characteristics have been investigated in a 113 mm diameter asymmetric rotating disk contactor of the pilot plant scale for two different liquid–liquid systems. The effects of operating parameters including rotor speed and continuous and dispersed phase velocities on the volumetric overall mass transfer coefficients are investigated. The results show that the mass transfer performance is strongly dependent on agitation rate and interfacial tension, but only slightly dependent on phase flow rates. In this study, effective diffusivity is used instead of molecular diffusivity in the Gr?ber equation for estimation of dispersed phase overall mass transfer coefficient.The enhancement factor is determined experimentally and there from an empirical expression is derived for prediction of the enhancement factor as a function of Reynolds number. The predicted results compared to the experimental data show that the proposed correlation can efficiently predict the overall mass transfer coefficients in asymmetric rotating disk contactors.     

表面活性剂-油-水体系界面张力的分子热力学模型

An interracial equation of state based on perturbation theory for surfactant-oil-water system has been developed. By comblninE the interracial equation of state with Boudh-Hir and IViansoori‘s model, a molecular thermodynamic model has been proposed. The interracial tension of surfactant-oil-water systems can be calculated from the surface tensions of pure oil and water by this model. The interfacial tension data for sodium dodecyl sulphate-heptane-water system, polyoxyethylene n-octylphenol-heptane-water system and hexadecyl trimethyl ammonium bromide-heptane-water system have been correlated. By using the adjustable parameters obtained, the interfacial tensions of these systems at other temperatures have been predicted. Both the correlated and the predicted values are sstisfactorv.     

Effect of salts and their interaction with ingenious surfactants on the interfacial tension of crude oil/ionic solution

Understanding the roles of asphaltene and resin as natural surfactants existed in crude oil can enlighten contradicting reported results regarding interfacial tension(IFT) of crude oil/aqueous solution as a function of salinity and ion type. In this way, this study is aimed to investigate the effect of these natural surface active agents on IFT of with special focus on SO_4~(2-)anion and Mg~(2+)cation. Two different synthetic oil solutions of 8 wt% of the extracted asphaltene and resin dissolved in toluene are prepared, and then IFT values are measured. After that,the obtained results are compared with the IFT of intact crude oil in contact with the same saline solutions examined in the previous stage. The obtained results showed a synergistic effect of Na_2SO_4+ MgCl_2 solution unlike the MgSO_4+ MgCl_2 and CaSO_4+ MgCl_2 solutions on IFT reduction of resin at MgCl_2 concentration of 15000 mg·kg~(-1). In summary, it is found that the affinity of asphaltene molecules towards the interface of oleic phase/ionic solution leads to higher IFT variation.     

Partition Behavior of Penicillin in Three-liquid-phase Extraction System

Partition behavior of penicillins G and V was studied in a novel three-liquid-phase extraction system, which is composed of butyl acetate (BA), polyethylene glycol (PEG), ammonia sulfate [(NH4)2SO4] and water (H2O). The main components in the top, middle and bottom phases are butyl acetate, polyethylene glycol aqueous solution and ammonia sulfate aqueous solution, respectively. Some parameters such as partition coefficients Di/j and mass fractions Ei of penicillins G and V were determined at the room temperature, respectively. Experimental efforts have been made to investigate the partition behavior of penicillin in the three-liquid-phase extraction system, including initial concentrations of phase-forming components [PEG and (NH4)2SO4], PEG molecular weight, pH, initial concentration of penicillin. The results indicated that penicillins G and V have the similar partition behavior. They preferentially distribute into the middle phase with the increase of initial concentration of phase-forming components and into the top phase with the decrease of pH, while partition coefficient Dm/b is hardly affected by pH value. The variation of PEG molecular weight has little effect on mass fractions of penicillin. The increase of initial concentration of penicillins G and V could lead to the increase of Dt/b, Dm/b and the decrease of Dt/m, while their mass fractions in all phases were almost independent on their initial concentrations.     

孤东原油组分的界面张力测定

按常规四组分分离法将孤东1#原油分离为饱和分、芳香分、胶质、沥青质,它们在原油中的质量分数分别为:45 88%,22 45%,14 73%,14 43%。将各组分在原油中所占的质量分数的十分之一和煤油配制成模拟油,模拟油与蒸馏水、碱水〔w(Na2CO3)=1 2%)〕体系的界面张力分别为:35 700,13 360;24 520,4 630;22 760,5 610;19 380,0 056mN/m。并对各分离组分进行了红外光谱、元素组成、相对分子质量测定。结果表明:界面张力的大小与各组分中的含氧量有关,含氧量越高,界面张力越低。沥青质是孤东1#原油的主要活性物质;w(沥青质)=3%时,模拟油与碱水〔w(Na2CO3)=1 2%〕体系的界面张力为0 0053mN/m。     

沥青质模型油/MD膜驱剂溶液的界面张力

从MD膜驱剂与原油界面活性组分沥青质模型油的界面张力出发,考察了作用时间、水相pH、MD膜驱剂质量浓度、盐浓度、沥青质含量、芳香度、温度等对模型油/水界面张力的影响,并根据扩散控制机理解释了动态界面张力初期过程,进一步揭示了MD膜驱油技术的机理。结果表明,沥青质模型油/MD膜驱剂溶液的界面张力先随时间增加而降低,约15min后达到平衡,达到平衡之前的过程基本上符合扩散控制过程;MD膜驱剂的加入并不能改变pH对模型油/水界面张力的影响趋势;在所考察的条件范围内,沥青质模型油/水溶液的界面张力不随MD膜驱剂质量浓度增加而改变,其值约为19 65mN/m;NaCl对界面张力的影响不明显;沥青质质量浓度从0增加到1000mg/L时,模型油/水和模型油/MD膜驱剂溶液的界面张力分别从23 4mN/m和22 0mN/m逐渐下降至20 0mN/m和18 8mN/m;温度从25℃升高到45℃时,模型油/水溶液的界面张力降低;但芳香度从0增加到100%时,其界面张力均从21 0mN/m增加至31 5mN/m。MD膜驱剂是表面非活性物质,在驱油时不存在低界面张力提高采收率的机理。     

原油组分对采出水乳状液稳定性的影响

采用界面张力仪、表面粘弹性仪和浊度仪,研究了原油组分对桩西采出水乳状液稳定性的影响.结果表明,当各组分在模拟油中的浓度相同时,沥青质的界面张力最小,蜡组分的最大,胶质的居中;在相同的剪切速率下,沥青质的界面剪切粘度最大,蜡组分的最小,胶质的居中.原油组分浓度增加,组分模拟油油水界面张力减小,界面剪切粘度增加,乳状液稳定性增强.分离组分模拟油乳状液稳定性的强弱顺序依次为:沥青质组分>胶质>蜡组分.     

以不同减渣为原料制备大庆油田复合驱用表面活性剂的可行性研究

为扩大大庆油田复合驱用表面活性剂的原料范围,降低表面活性剂的生产成本,研究了利用不同的减渣制备复合驱用表面活性剂的可能性。实验结果表明,利用大庆减渣制备出的OCS表面活性剂具有很好的界面活性,当OCS表面活性剂浓度为0·1%~0·3%,Na2CO3浓度在0·6%~1·2%的范围内,OCS表面活性剂/Na2CO3体系与大庆原油之间的界面张力可达到超低(~10-3mN/m数量级)。大庆减渣适宜作为复合驱用表面活性剂的原料,而大港和石家庄减渣则不适宜。     

SDBS/SB复配体系界面性能及影响因素分析

研究了SDBS与SB在不同配比和浓度下油水界面张力的变化情况,确定了复配体系的最佳配比和浓度;同时,考察了pH值和NaCl含量对最佳复配体系油水界面张力的影响。结果表明,当SDBS:SB为7:3,浓度为0.4%时,SDBS/SB复配体系的油水界面张力降至0.05mN/m,达到高效表面活性剂驱超低界面张力的要求。在pH值调节范围内,升高pH值,油水界面张力先降低后升高,当pH值为8时,油水界面张力降至0.04mN/m。加入少量的氯化钠时,油水界面张力先降低,当含盐量0.3%时,油水界面张力降至最低值0.02mN/m,后逐渐升高。     

XSY-11双子表面活性剂提高采收率应用研究

通过测定双子表面活性剂与原油的界面张力,发现双子表面活性剂在缺碱的条件下,也可以使油水界面张力降低至超低的能力,证明了其对碱的依赖性较小,优于普通表面活性剂.单独使用双子表面活性剂或者与其他表面活性剂协同使用,均可以使多种原油-水界面张力降低至超低范围.对双子表面活性剂溶液浓度等因素对油水界面张力的影响程度进行了分析.发现双子表面活性剂降低油水界面张力的能力主要与表面活性剂和油的性质密切相关.研究了其界面张力行为,发现双子表面活性剂具有比普通表面活性剂较高的界面活性,并且与盐具有很好的协同性,可以在较宽的盐度和表面活性剂浓度范围内降低油水界面张力至超低范围.     

餐厨废弃油脂合成的生物油磺酸盐与碱复配的界面性能

利用餐厨废弃油脂经磺化反应合成了生物油磺酸盐,并与碳酸钠进行复配,测定了复配体系的界面活性、动态界面张力、界面张力稳定性和分配性能。结果表明,生物油磺酸盐的平均分子量为393,属于水溶性;生物油磺酸盐与碳酸钠的复配体系具有较宽的界面活性范围和较好的界面张力稳定性。在碳酸钠质量分数为0.4%~0.8%范围内,能降低油水界面张力至10~(-3)m N/m。随着碳酸钠质量分数增加,复配体系与原油的最低界面张力呈现先减小后增大的趋势,碳酸钠最佳质量分数为0.6%。放置90 d后,最低界面张力基本上保持在10~(-3)m N/m。碳酸钠质量分数一定时,随着生物油磺酸盐质量分数增加,生物油磺酸盐在油水两相中的分配系数降低,当质量分数大于0.25%后,分配系数降幅变小。生物油磺酸盐质量分数一定时,随着碳酸钠质量分数增加,生物油磺酸盐在油水两相中的分配系数增大,增幅较小。     

Influence of Oil Properties on Bed Coalescence Efficiency

Abstract

Bed coalescence efficiency of oil separation from formation water was studied on model systems involving 10 real samples of crude oil and its fractions of different characteristics. Oil components were varied and all other parameters were kept constant, and high mineralization water served as the continuous phase. All experiments were realized on a commercial WO/O4 two-stage bed coalescer. Temperature, oil content, and fluid velocity were kept constant for all samples. Model emulsion was dispersed by constant stirring during the experiment to obtain primarily droplets of 20 μm diameter. Correlations for predicting the coalescence efficiency as a function of some physical and chemical oil properties are presented. The investigated oil components ensured a wide span of viscosity, density, and interfacial tension. The influences of mean molecular weight, neutralization number, as well as the contents of n-alkenes, NSO, and aromatics on coalescence efficiency were analyzed. On the basis of the empirical dependences of coalescence efficiency on individual parameters obtained by regression analysis of the data, a general mathematical model was established.     

驱油阴/两性表面活性剂复配体系协同效应研究

针对某油藏A区块,利用阴离子/两性表面活性剂的协同作用,进而达到油水超低界面张力,且两性表面活性剂十二烷基甜菜碱在浓度为0.1%~0.5%的范围内,降低油水界面张力的效果达到10~(-2) mN/m数量级,在加入阴离子表面活性剂的条件下,复配体系可以使油水界面张力达到超低界面张力。通过探讨表面活性剂的总浓度以及复配比对油水界面张力的影响,最终得到阴离子/两性表面活性剂复配体系可在较高矿化度和较低的浓度(0.4%)范围内达到10~(-3) mN/m的超低界面张力,并在此基础上对两者的协同作用进行分析。     

Examination of the parameters governing oily soil removal from synthetic substrates

The rate of removal of mineral oil soils from model polyester sub-strates by the roll-up mechanism shows a marked dependence on nonionic surfactant concentration even above the critical micelle concentration (cmc). Similarly, although the solid/water interfacial tension is observed to be constant, the equilibrium oil/water inter-facial tension in these systems consistently decreases as the nonionic surfactant concentration is increased. The dependence of removal time and oil/water interfacial tension on surfactant concentration above the cmc is most pronounced for nonionic surfactants having relatively high cmc. At a given concentration, surfactants exhibiting the lowest equilibrium oil/water interfacial tension generally provide the most effective soil removal, suggesting that the reported depen-dence of removal time on surfactant concentration is related to the commensurate lowering of the oil/water interfacial tension. Nonyl phenol ethoxylates perform exceptionally well with mineral oil on polyester substrates because of the combination of a low oil/water interfacial tension and high solid/water adhesion tension. Regardless of surfactant structure, mineral oil on Teflon FEP maintains a high contact angle in the water because the solid/oil interfacial tension is less than the solid/water interfacial tension. Oil removal in such systems occurs only by an inefficient necking and drawing process. Oleyl alcohol displays a high contact angle in the water on both Teflon FEP and Mylar substrates for reasons similar to that of mineral oil on Teflon FEP. Partial oil removal occurs from both substrates in selected built systems, presumably because a low oil/ water interfacial tension promotes necking and drawing. Given sufficient time, unremoved oils develop a liquid crystalline phase which results in slow oil removal via dispersion. Triolein soils also possess a relatively low solid/oil interfacial tension and similarly exhibt a high contact angle (in water) on both Teflon FEP and Mylar substrates in unbuilt surfactant systems. Builder addition lowers the oil/water interfacial tension and thereby prompts necking and drawing action.