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.     

TRANSIENT INTERFACIAL TENSION BEHAVIOR BETWEEN ACIDIC OILS AND ALKALINE SOLUTIONS

A study of the dynamic interfacial tension behavior of reacting acidic oil/alkaline solutions has been conducted for both an artificially acidified synthetic oil and a real crude oil for four different alkalis at various concentrations. The IFT values between a 10 mM acidified synthetic oil and various 25 mM alkaline solutions, before the minimum IFT value was reached, were found to be in the descending order: KOH, NaOH, Na₂SiO₃ and LiOH. The corresponding IFT values between diluted Lloydminster heavy crude oil and the same alkaline solutions, again before the minimum was reached, were found to be in the descending order: LiOH, NaOH, Na₂SiO₃ and KOH. The crude oil exhibited lower minimum IFT values against alkaline solutions than the synthetic acidified oil. The general trend of decreasing IFT towards a minimum value followed by an increase in IFT thereafter was noted for all solutions tested.     

THE EFFECT OF EQUILIBRATION TIME AND TEMPERATURE ON DROP-DROP COALESCENCE OF WILMINGTON CRUDE OIL IN A WEAKLY ALKALINE BRINE

The interfacial behavior of a Wilmington crude oil was studied as part of our investigations of enhanced oil recovery by weakly alkaline solutions. For some systems, the spinning drop apparatus can be used to measure transient interfacial tension (IFT) effects, coalescence times of oil drops, and film rigidity simultaneously, for rapid screening of chemical slug composition for the potential of improving oil recovery by the mechanisms of oil mobilization and oil bank formation. The experimental results presented include the effects of temperature, surface age, salinity, added surfactant, and polymer on coalescence time, film rigidity, and IFT behavior. Oil displacement tests were performed using surfactant-enhanced bicarbonate solutions formulated for improved mobility control and for improved oil mobilization and oil drop coalescence.

The most significant result of this work was that we were able to measure the dynamics in IFT between 2 coalescing oil drops as perturbations in the equilibrium concentration of surfactant at the interface occurred during film drainage. The accuracy of the technique for measuring IFT and film rigidity improved as the contact radii between the oil drops increased.     

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.     

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.     

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.     

Study on the Adaptability of Alkanolamide (LDEA) Lowering Oil/Water Interfacial Tension to Different Crude Oils

In order to investigate the high interfacial activity and fair oil phase adaptability of alkanolamide, “1:1” type lauric acid diethanolamide impurities (LDEA) were synthesized and purified by the column chromatography method to obtain dodecanoic acid diethanolamide (C₁₂DEA), ester mixture, etc. The exact structures of these compounds were further confirmed by IR, gas chromatogrph with mass spectroscopy (GC–MS), and NMR. The influence of each component on the interfacial tension of oil/water (IFT) was studied by systematic quantitative analysis. The results showed that (i) the strength of each system to reduce oil/water IFT is C₁₂DEA /DEA ≈ LDEA > C₁₂DEA/DEA/ESTER > C₁₂DEA/NaOH > C₁₂DEA > C₁₂DEA/ESTER > DEA. This indicates that LDEA contributes to the reduction of the oil/water IFT and the enhanced adaptability of crude oil in this order: DEA > > ESTER; (ii) when the IFT of the LDEA/DEA system reached an ultralow value, the minimum content of DEA in the system was 1%, and the maximum ester content was less than 5% when the LDEA/DEA/ESTER system reached the ultralow IFT; (iii) the possible mechanism of effect of LDEA components on the IFT and oil phase adaptability was proposed as the synergistic process among the hydrogen bonding, alkali effect, and interface self-assembly of molecules in the interfacial layer. The contribution of these three factors were hydrogen bonding > alkali effect > interface self-assembly.     

Effect of salinity and alcohol partitioning on phase behavior and oil displacement efficiency in surfactant-polymer flooding

The equivalent alkane carbon number (EACN) of a crude oil, namely Ankleshwar crude, is successfully modeled by a mixture of pure alkanes. The EACN of the crude oil is found to be 9.3, and an appropriate mixture of nonane and decane exhibited phase behavior similar to that of the crude oil. A surfactant system for a water flooded reservoir at 80 C and having a salinity in the range of 2% to 3% NaCl is formulated by blending a phosphated ester with a petroleum sulfonate in the weight ratio of 2/5. The addition of phosphate ester not only increases the salt tolerance of the petroleum sulfonate system, it also broadens the IFT minimum. The oil displacement tests at 80 C in sandpacks and Berea cores showed that the surfactant formulation containing tertiary amyl alcohol (TAA) displaced 92% oil in sandpacks and 79% crude oil in Berea cores. The oil recovery efficiency was poor when formulations contained other alcohols. From the effluent surfactant concentration, it is shown that there is a correlation between the tertiary oil recovery, surfactant breakthrough and surfactant retention in porous media. It is proposed that, because alcohols such as isopropyl alcohol (IPA), isobutyl alcohol (IBA) and secondary butyl alcohol (SBA) partition significantly in the equilibrated excess brine phase, the alcohol-depleted surfactant slug forms stable emulsions resulting in faster breakthrough of surfactant in the effluent and lower oil displacement efficiency. In the case of TAA-containing formulation, there is a partitioning of TAA in the oil phase. Therefore, there is a mass transfer of alcohol from surfactant slug to the oil ganglia in porous media. This produces a transient ultralow IFT between residual oil and the surfactant solution which mobilizes oil, resulting in higher oil displacement efficiency. Presented in part at International Symposium on Oilfield and Geothermal Chemistry, June 1983, in Denver, CO.     

Influence of Sophorolipid Structure on Interfacial Properties of Aqueous-Arabian Light Crude and Related Constituent Emulsions

Sophorolipids (SLs) offer an “environmentally friendly” alternative to chemically produced surfactants currently used in formulations for crude oil extraction, processing, and reclamation. Studies herein describe how sophorolipid structure influences its interfacial properties for environmentally and industrially relevant oil–water systems where the oil phase is Arabian light crude oil, paraffin oil, decane, hexadecane, a 1:1 vol/vol mixture of o-xylene and 1,2-dimethylcyclohexane, or a mixture of paraffin oil, o-xylene, and 1,2-dimethylcyclohexane (synthetic crude oil). SL-hexyl ester (SL-HE) reduces the crude oil–water interfacial tension (IFT) by 57 and 91% at 0.001 and 0.5 mg/mL, respectively. Crude oil displacement tests reveal that SL-ethyl ester (SL-EE) and SL-HE contract a crude oil slick on water to about 20% of its starting volume allowing for easier burning of spilled crude oil on marine surfaces. Water retention and emulsion phase (e.g., o/w vs. w/o) are determined by SL-structure/concentration, oil concentration, and oil composition to understand their performance for crude oil transportation and clean-up. For the first time, w/o emulsions were obtained using SLs and their formation occurred after homogenization when the oil phase consisted of a 1:1 mixture of o-xylene and 1,2-dimethylcyclohexane. Generally, the performance of SL-esters in the above studies was superior to that using Triton X-100, a comparison nonionic surfactant. Hence, SL-esters offer a valuable platform for tuning interfacial properties to optimize surfactant performance.     

Interfacial properties of cationic and anionic Gemini surfactant mixtures

The possibility and the prospect of cationic/anionic (“catanionic”) surfactant mixtures based on sulfonate Gemini surfactant (SGS) and bisquaternary ammonium salt (BQAS) in the field of enhanced oil recovery was investigated. The critical micelle concentration (CMC) of SGS/BQAS surfactant mixtures was 5.0 × 10⁻⁶ mol/L, 1–2 orders of magnitude lower than neat BQAS or SGS. A solution of either neat SGS or BQAS, could not reach an ultra-low interfacial tension (IFT); but 1:1 mol/mol mixtures of SGS/BQAS reduced the IFT to 1.0 × 10⁻³ mN/m at 100 mg/L. For the studied surfactant concentrations, all mixtures exhibited the lowest IFT when the molar fraction of SGS among the surfactant equaled 0.5, indicating optimal conditions for interfacial activity. The IFT between the 1:1 mol/mol SGS/BQAS mixtures and crude oil decreased and then increased with the NaCl and CaCl₂ concentrations. When the total surfactant concentration was above 50 mg/L, the IFT of SGS/BQAS mixtures was below 0.01 mN/m at the studied NaCl concentrations. Adding inorganic salt reduced the charges of hydrophilic head groups, thereby making the interfacial arrangement more compact. At the NaCl concentration was above 40,000 mg/L, surfactant molecules moved from the liquid–liquid interface to the oil phase, thus resulting in low interfacial activity. In addition, inorganic salts decreased the attractive interactions of the SGS/BQAS micelles that form in water, decreasing the apparent hydrodynamic radius (D_{H, app}) of surfactant aggregates. When the total concentration of surfactants was above 50 mg/L, the IFT between the SGS/BQAS mixtures and crude oil decreased first and then increased with time. At different surfactant concentrations, the IFT of the SGS/BQAS mixtures attained the lowest values at different times. A high surfactant concentration helped surfactant molecules diffuse from the water phase to the interfacial layer, rapidly reducing the IFT. In conclusion, the cationic-anionic Gemini surfactant mixtures exhibit superior interfacial activity, which may promote the application of Gemini surfactant.     

表面活性剂同系物体系对原油界面张力的影响

分别从表面活性剂的亲油性和亲水性的二种性能 ,研究了复配型表面活性剂的性能及规律。在表面活性剂同系物复配的研究中 ,得出相对分子质量分布窄的表面活性剂不能与原油形成低的界面张力 ,但两种以上相对分子质量分布窄的表面活性剂按一定比例混合后 ,则可以与大庆原油形成超低界面张力。形成超低界面张力的表面活性剂平均当量范围为 410～ 430 ,相对分子质量、碱浓度和界面张力三者之间有一定规律 ,即表面活性剂平均相对分子质量增加 ,界面张力曲线向低浓度碱方向移动 ;平均相对分子质量降低 ,界面张力曲线向高浓度碱方向移动。相对分子质量分布是影响界面张力的又一因素 ,表面活性剂相对分子质量分布、原油中的碳数分布和界面张力可能存在某种特定联系。支链对降低界面张力方面比直链有更好的效果 ,表面活性剂相对分子质量越高 ,则油砂对其吸附量越大     

The performance of polymer solutions in enhanced oil recovery: studies on their rheological,interfacial, and porous media behaviors

Four polymeric solutions based on xanthan, high and low molecular weight sulfonated polyacrylamides, and hydrolyzed polyacrylamide were prepared in aqueous solutions and their behaviors in enhanced oil recovery applications were investigated. The effect of thermal aging on polymer solutions was evaluated through rheological measurement. Pendant drop method was also used for measuring the interfacial tension (IFT) between crude oil and brine containing different polymer solutions. Moreover, the zeta potential of the oil reservoir particles treated with oil and polymer was determined by electrophoresis method in a nano-zeta meter instrument. In addition, sand pack and core flooding setup were used for evaluating the effectiveness of the polymer solutions in porous media. Polymer solutions displayed non-Newtonian behavior in almost the whole range of the shear rate applied; a shear thinning behavior was seen. Furthermore, the aging of polymers in formation water decreased the shear viscosity of all the polymers. The oil/water IFT decreased by the addition of polymers to water. The effect of xanthan polymer on zeta potential value was greater than that of the three acrylamide-based polymers. According to sand pack tests, by increasing the polymer concentration, the incremental oil recovery initially increased up to a polymer concentration of 3,500 ppm and then started to fall. Recovery factor increased from 50 to 65 % using the polymer solution in core flooding experiments. By increasing the injection rate from 0.2 to 3 mL/min, the injected fluid had less time to sweep the pores and consequently the amount of recovered oil decreased.     

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.     

Experimental investigation on CO2-light crude oil interfacial and swelling behavior

A systematic series of experiments are designed and performed including interfacial tension(IFT) measurements concomitant with Bond(BN,the ratio of gravity forces to capillary forces) and swelling/extraction measurements.Dynamic IFT, BN and swelling/extraction are measured as a function of pressure at temperatures of 30,50 and 80 ℃.In addition, in the light of measured IFT the minimum miscibility pressure(MMP) of CO_2 and light crude oil is determined based on a method called vanishing interfacial tension(VIT). The obtained results interestingly revealed that equilibrium IFT decreases linearly with pressure in two distinct pressure intervals while equilibrium BN shows an increasing trend as a function of pressure for all of the studied cases while no obvious trend is observed for swelling of crude oil and extraction of light-components regarding time, temperature and pressure.     

A Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: The effects of pH,alkali and salt

A chemical equilibrium model is proposed to describe the effects of acid content, pH and sodium ion concentration on the interfacial activity of crude oil in aqueous alkaline solutions. The model is based on an equilibrium among the dissociation of acids in the crude, the dissociation of the sodium salt containing the active species and the dissociation of water. It is shown that once the pH of the interface reaches the pK_a of the acids, the interfacial tension (IFT) drops steeply and that further addition of sodium ions increases the IFT by shifting the equilibrium to form undissociated soap.     

Salt-Induced Constructions of Gemini-like Surfactants at the Interface and Their Effects on the Interfacial Tension of a Water/Model Oil System

It is an urgent issue to enhance oil recovery for unconventional reservoirs with high salinity. Focused on this topic, salt addition is a powerful tool to motivate the surfactant assembly at the water/oil interface and improve the interfacial activity. We used a cationic surfactant cetyltrimethylammonium bromide (CTAB) and an anionic salt dicarboxylic acid sodium (CnDNa) to construct gemini-like surfactants at the interface and evaluated their ability to reduce the interfacial tension (IFT) between model oil (toluene and n-decane, v:v = 1:1) and water. Interestingly, the fabrication of a (CTAB)₂/C4DNa gemini-like surfactant was hardly achieved at the fresh water/model oil interface, but accomplished at the brine/model oil interface. At a high NaCl concentration (100,000 mg L⁻¹), the IFT value is reduced to 10⁻³ mN m⁻¹ order of magnitude, which is generally desired in practical applications. The control experiments displacing the surfactant type and the spacer length further confirmed the NaCl effects on the interfacial assembly.     

Effects of Polyether Surfactants on Dynamic Interfacial Tension of Betaine Solutions against Crude Oil

The dynamic interfacial tension (IFT) of betaine and betaine/polyether‐nonionic surfactant‐mixed systems against hydrocarbons, kerosene, and crude oil–water was studied using a spinning‐drop tensiometer. The influence of average molecular weight of polyether‐nonionic surfactants on IFT of mixed solutions was investigated. On the basis of the experimental results, one can find that it is difficult to reach the ultralow IFT value for betaine solution against hydrocarbon and kerosene because of the mismatch between the hydrophobic and hydrophilic groups. After purification, kerosene still contains a small amount of carboxyl groups, which can exert a synergistic effect on surfactants resulting in a lower IFT. The IFT of betaine and mixtures against Daqing crude oil can reach an ultralow value because of the mixed adsorption of surfactant and petroleum soap molecules. For mixed solutions, with the increasing concentration of added polyether, the decrease of petroleum soaps at the oil–water interface results in the destruction of synergistic effects.     

Model Development for MEOR Process in Conventional Non‐Fractured Reservoirs and Investigation of Physico‐Chemical Parameter Effects

A three‐dimensional multi‐component transport model in a two‐phase oil‐water system was developed. The model includes separated terms to account for the dispersion, convection, injection, growth and death of microbes, and accumulation. For the first time, effects of both wettability alteration of reservoir rock from oil wet to water wet and reduction in interfacial tension (IFT) simultaneously on relative permeability and capillary pressure curves were included in a MEOR simulation model. Transport equations were considered for the bacteria, nutrients, and metabolite (bio‐surfactant) in the matrix, reduced interfacial tension on phase trapping, surfactant and polymer adsorption, and effect of polymer viscosity on mobility of the aqueous phase. The model was used to simulate effects of physico‐chemical parameters, namely flooding time schedules, washing water flowrate, substrate concentration, permeability, polymer and salinity concentration on Original Oil In Place (OOIP) in a hypothetical reservoir.     

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.     

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.