疏水缔合聚合物驱体系中原油乳状液性质及破乳规律

采用瓶试法考察了原油组成及疏水缔合聚合物（Hydrophobically associating polymer, HAP）质量浓度对原油乳状液稳定性的影响,用油 水界面张力、界面电性、界面扩张流变、界面剪切黏度等多个参数表征了HAP驱采出液油 水界面性质的变化规律,用一系列酚胺树脂聚醚破乳剂对模拟采出液进行破乳。结果表明,原油中胶质和沥青质是影响原油乳状液稳定的重要因素;实验浓度范围内,随着HAP浓度升高,原油乳状液稳定性增强。HAP具有界面活性,吸附在油 水界面可降低界面能,利于乳化;HAP在界面上形成交联网状结构,提升了界面膜的扩张模量和剪切模量,同时增强了界面膜的负电性,利于稳定乳状液。环氧乙烷与环氧丙烷各占一半的酚胺树脂聚醚破乳剂与1%甲苯二异氰酸酯（TDI）交联后,5 min即可完全将原油乳状液破乳。     

炼油厂水包油型乳状液破乳研究

针对我国原油在加工过程中产生的水包油型乳状液进行了破乳研究。讨论了此类乳状液的形成主要是由于分散相油滴表面带负电荷，形成Ｓｔｅｒｎ层，油滴相互排斥，形成了稳定的乳状液。进行了破乳剂的评选，评选出ＨＳＧ系列中阳离子破乳剂对此类乳状液有好的破乳效果。讨论了阳离子破乳剂的组成对破乳效果的影响，ＨＳＧ、ＨＳ系列阳离子破乳剂中，分子含氮原子数量多，所带的正电荷多，电中和能力强，破乳效果好，进行了破乳机理的探     

以非离子型乳化剂为原料制备油包水型有机硅乳液

为获得稳定的有机硅乳液,分别采用几种不同亲水亲油平衡值的非离子型乳化剂(Gransurf 71,77,90,Span 60,Tween85)制备了有机硅乳液。考察了乳化剂Gransurf 77(R77)浓度、乳化剂并用、油水质量比、环境温度对有机硅乳液类型、液滴尺寸、黏度及稳定性的影响。采用乳化剂R77与R71复配获得了液滴尺寸小、稳定性较好的乳液。研究表明,随着乳化剂浓度的增加,液滴尺寸减小,乳液的稳定性提高;与含水量50%的乳液相比,高含水量乳液的液滴尺寸较小,黏度增加;乳液在室温下稳定,70℃时稳定性降低。     

微波-磁性纳米Ni粉对稠油破乳效果的pH值响应性

通过瓶试法研究了不同pH值下有/无微波辐射时磁性纳米Ni粉对稠油水包油(O/W)型乳状液破乳效果的影响规律,在此基础上,结合油滴形貌和分布以及乳状液表观黏度揭示了微波 磁性纳米Ni粉破乳效果的pH值响应行为机理。结果表明：当pH值相同时,单纯磁性纳米Ni粉和微波-磁性纳米Ni粉作用下的乳状液的分水率都随着磁性纳米粒子浓度的增加先上升后下降;与此同时,磁性纳米Ni粉与微波具有协同破乳的作用,且随着pH值增大,微波与磁性纳米Ni粉的耦合作用先减弱后增强,在pH值为3时两者的耦合作用最强,该条件下乳状液的分水率在30 min时达到102.63%。     

APPLICATION OF PETROLEUM DEMULSIFICATION TECHNOLOGY TO SHALE OIL EMULSIONS

Demulsification, the process of emulsion separation, of water-in-oil shale oil emulsions produced by several methods was accomplished using commercial chemical demulsifiers which are used typically for petroleum demulsification. The shale oil emulsions were produced from Green River shale by one in situ and three different above-ground retorts, an in situ high pressure/ high temperature steam process, and by washing both re tort-produced and hydrotreated shale oils.     

APPLICATION OF PETROLEUM DEMULSIFICATION TECHNOLOGY TO SHALE OIL EMULSIONS

ABSTRACT

Demulsification, the process of emulsion separation, of water-in-oil shale oil emulsions produced by several methods was accomplished using commercial chemical demulsifiers which are used typically for petroleum demulsification. The shale oil emulsions were produced from Green River shale by one in situ and three different above-ground retorts, an in situ high pressure/ high temperature steam process, and by washing both re tort-produced and hydrotreated shale oils.     

Effect of polar head surfactants on the demulsification of crude oil

Surfactants can act as demulsifiers to neutralize the stabilizing effect of natural emulsifiers in crude oil. Here, the effect of polar head group of surfactants with identical hydrophobic chain C₁₂ (SLES, SLS, C₁₂E₂₃, BKC, C₁₂E₇) on the demulsification of crude oil emulsion and its effect on water separation rate were studied at different temperature. The activation energy for destabilization was calculated. The results indicate that the rate of water separation increases with temperature and surfactant concentration. The emulsion destabilising activation energy decreases as the concentration of the surfactant increases. The Interfacial Tension (IFT) study showed that when the reduction in IFT was the highest, the water separation rate and efficiency achieved was the highest.     

Resolution of water in crude oil emulsion by some novel aromatic amine polyesters

In this work, three aromatic amines (p-toluidine, p-nitroaniline and p-chloroaniline) were chosen as bases for the repatriation of some nonionic polyesters. These amines were ethoxylated with different total number of ethylene oxide units 6, 12, 18. The prepared ethoxylated amine diols were polyesterified with maleic anhydride and polypropylene oxide polyethylene oxide block copolymers in polyesterification reaction. The demulsification efficiency of these demulsifiers was investigated using the bottle test. The effects of the molecular weight, concentration, asphaltene content, water content, Hydrophile Lipophile Balance (HLB) and temperature on the demulsification efficiency were investigated. The surface active properties were correlated with their demulsification efficiency. It was found that, NAE₁₈D gave the best result in the demulsification process. The demulsification efficiency was discussed on the light of surface active properties, interfacial tension and the factors affecting the demulsification. The surface-active properties of the prepared demulsifiers were measured at 60 °C.     

驱油剂对三元复合驱采出液破乳脱水的影响

研究了驱油剂对三元复合驱模拟采出液破乳脱水效果的影响规律,单一的碱、表面活性剂和聚合物对脱水率和水色有较大的影响;3种驱油剂之间存在明显的协同作用,对脱水率和脱出水色的影响很大.显微照片验证了含驱油剂的乳液存在多重乳状液.根据破乳机理和三元复合驱采出液的特点,提出了合成新型破乳剂的研究思路.     

Optimum demulsifier formulations for Nigerian crude oil-water emulsions

The formation of crude emulsion during oil production and processing is a challenge of significant proportions to the oil producers. Studies show that about two third of Nigerian crude oil production is in form of water in oil emulsion. For economic and operational reasons, it is necessary to separate the water completely from the crude oil before transportation or refining.Efficiency of separation of crude emulsions is of major importance to producers. To this end, this study primarily seeks to investigate the formulation of effective demulsifier that can be used to achieve this aim; and in so doing, the optimal separation efficiency attainable by this demulsification process is determined. Six different samples of water and oil soluble demulsifiers were used on two different samples of synthetic emulsion (sample I and II (both water in oil emulsion) from different Nigerian oil fields). The bottle test method was used to determine the percentage water separation for each crude oil emulsion/chemicals (demulsifiers) mixture. The concentrations of the combined six chemicals (demulsifier samples A–F) in the mixture were related to the percentage water separation using response surface methodology central composite design (RSMCCD).Results show that the optimum concentrations of demulsifiers A–F are 59?ppm/39?ppm/29?ppm/20?ppm/29?ppm/13?ppm respectively for crude oil sample I. While 54?ppm/40?ppm/25?ppm/21?ppm/29?ppm/8?ppm respectively were observed as optimum concentration for crude oil II. The combination of these chemical was observed to return better performance than the existing commercial demulsifiers with percentage water separation of 92% and 94% compared to percentage water separation of 87% and 90% returned by one of the currently available demulsifier used in the petroleum industry for crude oil A and B respectively. Hence, the need to carry out optimization analyses on different emulsified crude oil cannot be over-emphasize.     

Influence of polymers on the stability of Gudao crude oil emulsions

The influence of different types and concentrations of polymers on the stability of Gudao crude oil emulsion was investigated by measuring the volume of water separated from the emulsions and the interfacial shear viscosity of the oil/water interfacial film. Experimental results indicate that the simulated water-in-oil emulsion with 40 mg/L of partially hydrolyzed polyacrylamide （HPAM） 3530S could be easily broken by adding demulsifier C and was readily separated into two layers. However, HPAM AX-74H and hydrophobically associating water-soluble polymer （HAP） could stabilize the crude oil emulsion. With increasing concentration of AX-74H and HAP, crude oil emulsions became more stable. Water droplets were loosely packed in the water-in model oil emulsion containing HPAM 3530S, but water droplets were smaller and more closely packed in the emulsion containing AX-74H or HAP. The polymers could be adsorbed on the oil/water interface, thereby increasing the strength of the interracial film and enhancing the emulsion stability.     

水解聚丙烯酰胺对原油破乳的影响

采用紫外光降解法制备了4种不同黏均相对分子质量(Mη)的聚合物溶液,并用其配制不同质量浓度的含该聚合物的原油乳液。通过测定原油乳液脱水率、界面张力和分配系数,考察了聚合物质量浓度、黏均相对分子质量及聚合物种类对原油破乳的影响。实验结果表明,聚合物种类及其黏均相对分子质量是影响原油破乳的主要因素。对于水解聚丙烯酰胺(LDHPAM),当Mη1.14×106时,相对于空白样,它对原油乳液稳定性有明显的增强作用;当Mη1.14×106时,它对原油乳液稳定性无明显影响;与LDHPAM相比,疏水缔合聚合物(AP-P4)由于分子中含有少量的疏水基团,更易吸附于油水界面,对原油乳液稳定性的影响较为显著,当AP-P4质量浓度大于等于300mg/L时,原油乳液在55℃下静置2h后的脱水率仅为20%,远低于LDHPAM的60%。     

Demulsification of Crude Oil Emulsion via Ultrasonic Chemical Method

Abstract

Lots of water and surfactants are poured into the oil well to enhance the exploiting efficiency, so the crude-oil emulsions exploited by this technology contain much water, which is very hard to be separated at present. The demulsifying and separating experiments of the crude-oil emulsion were conducted by using the thermal chemical method and the ultrasonic chemical method separately. The crude oil emulsion samples were provided by the Dagang oil field of China and the water content was 35% volume/volume (v/v). The key influencing factors on demulsification effect were explored by changing the ultrasonic output power, the irradiating time, and the demulsifier amount in the experiments. The dehydrating ratios were compared among the self-made emulsions of different water content with the ultrasonic chemical method. The demulsifying velocity and dehydrating ratio for the high water content crude-oil emulsion was better than that of the emulsion with lower water content in the demulsifying experiments with the ultrasonic chemical method. For the crude-oil emulsion used in this experiment, the result was a dehydrating ratio of 97.7% under the condition of 100 W of ultrasonic output power, 10 min of irradiating time, 50 mg/L of demulsifier, and 75°C of water bath temperature.     

Demulsifier performance at low temperature in a low permeability reservoir

The crude oil in Longdong area is produced in the form of emulsion containing associated oil and water, which needs to be separated before dispatch to end user. Chemical demulsification under high temperature is the most widely used technology to break the emulsions. In this study a rheological method was used to determine the curve of viscosity-temperature and lower limit of temperature was determined. A series of experiments on low-temperature commercial demulsifies were implemented for studying demulsification performance by bottle test method. Mechanism of low-temperature demulsifier was studied by using spinning drop interfacial tensiometer to determine interfacial tension between the crude oil and demulsifier solution by considering the concentration. Turbiscan stability analyzer was used to study the effect of water content, temperature, and demulsifier concentration on emulsion stability. The corresponding relationship between interfacial tension and demulsification was verified through the study of low-temperature demulsifier effect on interfacial tension. Efficient low-temperature demulsifiers AR102, AR901, PR929, and PRC06 were selected. PRC06 was chosen to be the best at 40°C, and when the optimal concentration was 200 mg/L, dehydration rate was 99.51%.     

An evaluation of lignocellulosic solutions from OPEFB pulping process as demulsifiers for crude oil emulsion demulsification

Lignocellulosic solutions from oil palm empty fruit bunch (OPEFB) organosolv pulping process are used as demulsifiers for demulsification of crude oil emulsion using a model of water-in-oil emulsion of crude oil and brine solution. The results indicate that the demulsification performance was favored when only lignin compound was contained in the demulsifier. The phase separation capacity and rate were strongly affected by brine pH values, temperatures and demulsifier dosages. Complete phase separation capacity was achieved at the optimum conditions. The separated oil and water are qualified for refining process and water treatment, respectively, making it promising as a demulsifier.     

Synthesis and evaluation of some new demulsifiers based on bisphenols for treating water-in-crude oil emulsions

The present paper endeavors to synthesize nine types of demulsifiers based on bisphenols (bisphenol A (BA), bisphenol AC (BAC) and bisphenol CH (BCH)) having different ethylene oxide units (n = 27, 34, 45) namely; E (x + y) (where E represents BA, BCH or BAC and (x + y) which represents the ethylene oxide units (27, 34, 45)). The chemical structures of the prepared demulsifier were elucidated using FT-IR and ¹H NMR spectra. Effect of the chemical structure (hydrophobic and ethoxylated degree of hydrophilic parts) and the mechanism of demulsification process was investigated. The data were discussed on the light of the chemical structure of the demulsifiers and the factors, effecting the demulsification process. The efficiency of these demulsifiers was tested on water-in-oil emulsions (w/o) at different concentrations (100, 200 and 300 ppm), 7.4% asphaltene content and 30%, 50% and 70% water content. From the obtained data the best demulsifier was E(34)BA which shows 100% demulsification after 58 min at 30% water content and 300 ppm of the demulsifier.     

Demulsification of Asphaltene-Stabilized Emulsions—Correlations of Demulsifier Performance with Crude Oil Composition

Model asphaltene-stabilized emulsions are used to study the impact of oil composition on the efficiency of demulsification. Varying ratios of toluene and heptane, mixed with asphaltene extracted from a Gulf of Mexico crude oil, were mixed with water to produce emulsions that exhibited characteristic coalescence (water drop) rates. Commercial demulsifiers of varying types and chemistries were added to these emulsions, and resultant rates of water drop measured and compared. Emulsion stability and demulsifier effectiveness are shown to be highly dependent on overall aromaticity of the crude as measured by hydrogen-to-carbon molar ratio. Correlations of observed behavior with actual crude emulsions and demulsifier performance were observed and are reported.     

典型高酸原油乳化原因与破乳新方法

研究高酸原油乳化原因,对开发破乳效果更好的破乳剂意义重大。通过对荣卡多、多巴和阿尔巴拉克3种典型高酸原油的乳化特性研究发现,当前常用的破乳剂效果较差,油 水混合强度和洗盐水pH值显著影响高酸原油的破乳效果,采用酸性助剂和螯合助剂方法可以大幅提高破乳剂的效果。     

微观液滴分布对含蜡原油乳状液流变性的影响

通过显微镜观察并拍摄原油乳状液的微观结构图像,研究了乳状液体系分散相液滴大小及分布规律,以及微观液滴分布对乳状液体系流变性的影响机理。W/O型原油乳状液中含水率增加,引起内相液滴个数增多,小液滴所占的比例减小,相对大的液滴所占的比例增大;搅拌转速的增大,使体系内相液滴个数增多,平均液滴直径减小。通过测试在固定搅拌条件下制备的不同含水率的3种含蜡原油乳状液在原油凝点附近温度屈服特性和触变性等流变特性,可以发现随含水率的增大,乳状液体系屈服应力增大、触变性增强,且含水率越高,变化的趋势越明显。通过测试不同搅拌转速下制备的含水率为30% 的原油乳状液在原油凝点附近温度的触变性,可以看出随搅拌转速的增大,体系经受同等剪切速率剪切时对应的剪切应力增大、触变性增强。进一步建立了屈服应力与测试温度、含水率之间的关系式,其平均相对误差为9.83%。     

无机盐对乳状液破乳效果的影响

研究了无机盐对乳状液破乳的影响。结果表明，极少量的无机盐能有效地加速W／O型乳液的破乳，提高破乳脱出水的透光率。特别是NaCl或KCl存在时，在90℃油浴中加热60min后，5ml乳状液的剩余体积分别为0．02、0．07ml(即0．4％、1．4％)，破乳效率明显高于不含无机盐的乳状液。对于O／W型乳状液，极少量的无机盐也能有效地加速其破乳，其中AlCl3的破乳效率最高，在90℃油浴中加热10min，乳状液全部破乳。不同种类的盐对乳状液破乳脱出水的透光率影响不同。无机盐对乳状液破乳效率的影响与离子价态和水合离子半径有关。