辽河油田稠油O/W乳状液的破乳实验

实验考察了TA-1、TA-3、BP-6、SP-1,SP-2、AE-3、TG-1、THO-A2、THG-A3等12种商用破乳剂对辽河油田稠油乳状液的破乳效果,并考察了破乳剂的复配破乳效果.结果表明:THG-A2、TA-1两种破乳剂破乳120 min后,稠油乳状液脱水率可以达到80%;THG-A2/SP-2在复配质量比1:2、投放量为0.3～0.35 g/L、破乳温度为60～65℃时复配处理效果最佳,采用该复配剂破乳120 min后,脱水率可高达98.7%.此外,本文通过高速摄像观察了稠油乳状液的破乳过程,并对其破乳机理进行了分析.     

油水乳状液的稳定机理及其化学破乳技术的研究进展

油/水乳状液的破乳是重油生产和加工过程的重要环节,破乳剂的研发一直是油田化学中重要的研究内容。本文综述了国内外化学破乳剂研发的现状与趋势,阐述了重油中以沥青质为主的天然乳化剂的结构特点,深入分析了沥青质在油水乳状液的形成与稳定的过程中所起到的关键性作用,揭示了油水乳状液的形成与稳定性机理。进一步论述了具有普适性强、无毒、可生物降解且价格低廉的天然高分子破乳剂的破乳作用及其最新研究结果。重点介绍了微吸液管技术和原子力显微镜技术等现代分析手段在油水乳状液破乳过程中对相关微观机理研究的重要应用。     

原油乳状液的稳定性及新型破乳剂的研究

介绍了原油乳状液的形成条件,分析了原油乳状液中的天然乳化剂,如沥青质、胶质、石蜡及固体黏性颗粒对乳状液稳定性的影响,概括了破乳剂的破乳机理及几种研究应用较多的新型破乳剂.     

疏水缔合聚合物驱乳状液破乳规律研究

本文采用瓶试法考察了直链型、支链型及超支化型聚醚破乳剂及其与阳离子反相破乳剂协同作用对乳状液破乳效果的影响。结果表明,超支化聚酰胺-胺聚醚破乳剂与阳离子反相破乳剂协同作用对模拟疏水缔合聚合物驱乳状液有良好的破乳效果,随着聚醚破乳剂分子结构中环氧乙烷(EO)数增加,破乳效果增强,破乳剂最佳的EO/PO质量比为1/1。聚酰胺-胺聚醚破乳剂能显著降低油水之间的界面张力和界面扩张模量,表明该破乳剂分子易于在油水界面吸附,并破坏原乳状液界面膜的强度,从而有利于破乳。     

高含水原油的热化学破乳方法

针对高含水原油破乳中广泛采用的热化学法,试验研究了加热温度、加入破乳剂量对破乳效果和破乳速率的影响.试验结果表明,对一定量的原油乳状液,破乳剂用量均在一个最佳值;温度会影响破乳剂的最佳值,随温度升高,原油乳状液破乳时所使用的破乳剂用量的最佳值降低;同时,加入的破乳剂量对乳状液脱水速率也有一定的影响.     

破乳剂对原油乳状液界面膜作用机理研究进展

本文论述了原油破乳机理,同时综述了破乳剂对原油乳状液界面膜作用的研究进展.针对破乳剂在油水中的分配与破乳效果的研究现状以及原油破乳界面特性的研究现状,分析了影响原油乳状液稳定性的因素.     

热采用防乳破乳剂的研究与应用

稠油在热采高温作用下,容易在油层中发生乳化行为,形成稳定的油包水乳状液,给地面产出液处理流程造成一定的负担。通过分析热采放喷后产出液的含水率为28%、脱水原油的黏度为2 300 mPa·s、胶质与沥青质含量和为24.33%,从醇类、酚醛树脂类、多烯多胺类、复配类的防乳破乳剂中优选出防乳破乳剂PEC-12,幵分析了破乳温度、防乳破乳剂浓度、乳状液含水率对PEC-12防乳破乳剂破乳效果的影响。结果表明,随着破乳温度从50℃升高至80℃,防乳破乳剂的破乳率从44.6%逐渐升至98.2%。防乳破乳剂最经济有效的浓度为200ppm。乳状液中含水率从20%增至40%时,防乳破乳剂的脱水率从62.5%增至93.8%。矿场试验表明,在注热过程中添加防乳破乳剂是一种能有效抑制稠油反相乳化的有效措施,添加PEC-12防乳破乳剂后,地面处理流程显示油包水乳状液总量降低80%,稠油乳状液破乳效果好,处理负担明显减轻,同时跟地面产出液破乳剂发生了协同破乳作用,使处理后的污水中含油量达到设计要求,满足回注地层的水质要求。     

破乳-絮凝法处理O/W乳状液污水的实验研究

研究了大庆某油田O/W乳状液的油水分离特性,考查了自行研制的TS-24反相破乳剂对该乳状液的破乳效果.以模拟采出水为介质,采用小型装置开展了热化学除油实验.结果表明:TS-24在投加量为300 mg/L,脱水温度为50℃,停留时间为3h,模拟采出水除油率为94.5％.对实际三元复合驱采出水3h除油率为93.7％.破乳后对三元复合驱采出液进行絮凝沉淀,结果表明:处理后出水含油量低于500 mg/L,悬浮物质量浓度低于200 mg/L,符合污水排放标准.同时,考察了影响破乳剂破乳效果的因素,并对其机理进行了分析.     

原油乳状液的稳定与破乳机理研究进展

综述了原油乳状液中天然表面活性物质 ,如沥青质、胶质、固体颗粒物以及石蜡对原油乳状液稳定性的影响。讨论了原油破乳机理和破乳剂组成、HLB值等物化性质、破乳剂用量、复配与原油破乳脱水的关系。同时介绍了目前国内使用较多的几个系列破乳剂。     

热化学破乳对弱碱三元复合驱乳状液破乳效果影响研究

弱碱三元复合驱采出液乳化严重,油水分离的速度及程度,影响其经济效益.采用恒温静沉分离、多重光散射仪、脱水率等手段,研究了加热条件下清水型、聚醚型、多乙烯多胺型破乳剂对大庆油田某弱碱三元复合驱乳状液的破乳效果.结果 表明,在加热条件下,3类破乳剂对弱碱三元复合驱均有不同程度的破乳效果,3类破乳剂中100#(聚醚型)破乳剂的破乳脱水速率较快.温度越高,破乳速率越高,乳状液的分离效果越好,温度升高至55℃时,出现极值温度点,乳状液的破乳效果最好,温度继续升高,乳状液反而出现乳化现象.10#聚醚型破乳剂在10mg· L-1油相、水相具有良好的破乳效果,适合大庆油田某区块弱碱三元复合驱采出液破乳.     

Emulsification characteristics of three- and two-phase emulsions prepared by the ultrasonic emulsification method

Diesel engines exhausting gaseous emission and particulate matter have long been regarded as one of the major air pollution sources, particularly in metropolitan areas, and have been a source of serious public concern for a long time. The emulsification method is one of the potentially effective techniques to reduce emission pollution from diesel engines. Ultrasonic waves are a kind of sound waves with a frequency larger than 20 kHz, and they cannot be detected by the human ear. The phenomena of cavitation and hot spots produced by the rather violent action of ultrasonic waves can cause rapid chemical and physical reactions. This allows immiscible liquids to be well stirred with each other by means of ultrasonics. An ultrasonically vibrating machine that provides ultrasonic waves of a 40-kHz frequency was employed to prepare two- and three- phase emulsions in this experimental study. The fuel properties and the emulsion stability of the diesel emulsions were measured and analyzed. Experimental results show that the ultrasonic emulsification method successfully prepared two- and three-phase emulsions with tiny dispersed-phase droplets that are very evenly distributed in the outer oil or water phase. The ultrasonic processing time, quantity and HLB of the emulsifying agent were noted to have determinative influences on the formation of the emulsion and the fuel properties. A longer ultrasonic processing time caused less un-emulsified diesel fuel, smaller sizes and a more even distribution of dispersed-phase droplets in the outer oil phase and larger emulsion viscosity. However, a longer ultrasonic processing time also produced a larger temperature rise in the emulsion, leading to the deterioration of the emulsion stability. The O/W emulsion was found to have the lowest percentage of separation and thus the highest emulsion stability among the O/W/O, O/W and W/O emulsions. In addition, in comparison with the W/O emulsion, the O/W emulsion was shown to have a smaller size and a more even distribution of the dispersed-phase droplets. It also had a lesser rise in emulsion temperature when the ultrasonic processing time increased. The control of the ultrasonic processing time is important to successfully prepare the three-phase O/W/O emulsion. Too long a vibration time at the second-stage of emulsification is shown to cause the dispersed-phase pellets to contract and congregate with the inner-phase droplets. The three-phase emulsion structure then finally disappears and transforms into a two-phase emulsion. The addition of 2% by volume of the emulsifier mixture of Span80 and Tween80 with a HLB = 8, as suggested by this study for the preparation of stable two- and three-phase emulsions, were observed to have the lowest percentage of separation of the W/O and O/W/O emulsions. For preparing a stable O/W emulsion, the proportion of the emulsifier could be as low as 1.5% by volume. The percentage of separation of the O/W/O emulsion was lower and less influenced by the change in emulsion temperature than was the W/O emulsion with the same water content. However, the O/W/O emulsion was found to have a larger viscosity and a more significant variation of its viscosity, depending on the ultrasonic processing time, than the W/O emulsion.     

The fuel properties of three-phase emulsions as an alternative fuel for diesel engines

Diesel engines are employed as the major propulsion power for in-land and marine transportation vehicles primarily because of their rigid structure, low breakdown rate, high thermal efficiency and high fuel economy. It is expected that diesel engines will be widely used in the foreseeable future. However, the pollutants emitted from diesel engines (in particular nitrogen oxides and particulate matter) are detrimental to the health of living beings and ecological environment have been recognized as the major air pollution source in metropolitan areas and have thus attracted much research interest. Although diesel oil emulsion has been considered as a possible approach to reduce diesel engine pollutants, previous relevant applications were restricted to two-phase emulsions. Three-phase emulsions such as oil-in-water-in-oil briefly denoted as O/W/O emulsions and water-in-oil-in-water, denoted as W/O/W, have not been used as an alternative fuel for any combustion equipment. Studies on the properties of three-phase emulsion as fuel have not been found in the literatures. The emulsification properties of an O/W/O three-phase diesel fuel emulsion were investigated in this experimental study. The results show that the mean drop size of the O/W/O emulsion was reduced significantly with increasing homogenizing machine revolution speed. An increase in inner phase proportion of the O/W/O emulsion resulted in increasing the emulsion viscosity. The viscosity of O/W/O emulsion is greater than that for water-in-oil (denoted briefly as W/O emulsion) for the same water content. More stable emulsion turbidity appeared for three-phase O/W/O diesel emulsions added with emulsifier with HLB values ranging from 6 to 8. In addition, three-phase O/W/O emulsions with greater water content will form a larger number of liquid droplets, leading to a faster formation rate and greater emulsion turbidity at the beginning but a faster descending rate of emulsion turbidity afterwards. The potential for using O/W/O emulsions as an alternative fuel for diesel engines was also evaluated.     

Comparison of fuel properties and emission characteristics of two- and three-phase emulsions prepared by ultrasonically vibrating and mechanically homogenizing emulsification methods

Emulsions have long been considered as an alternative fuel for combustion equipment in order to achieve better fuel economy and pollution reduction. While a mechanical homogenizing method is frequently used to prepare emulsions, the use of an ultrasonic emulsification method to do so is still rather limited, and is mostly applied to two-phase emulsions only. Hence, two-phase W/O and three-phase O/W/O emulsions, prepared by a mechanical homogenizer and an ultrasonic vibrator, respectively, were prepared and used as engine fuel. The emulsion properties, engine performance, and engine emission characteristics between these two emulsification methods were measured and compared. The potential of the ultrasonic emulsification method was also evaluated. The experimental results show that the emulsions prepared by the ultrasonic vibrator appeared to have more favorable emulsification characteristics such as smaller dispersed water droplets that were distributed more uniformly in the continuous oil phase, lower separation rate of water droplets from the continuous phase of diesel fuel and thus a lower separating rate of the dispersed water droplets from the emulsion, larger emulsion stability, and larger emulsion viscosity than the emulsions produced using a mechanical homogenizer. In addition, a larger content of water was emulsified when the emulsion was prepared using the ultrasonic vibrator than the mechanical homogenizer. The emulsions prepared by the ultrasonic vibrator also had a lower fuel consumption rate, lower bsfc, and significantly lower CO emission while at the same time having a larger black smoke opacity. When comparing the two-phase W/O and the three-phase O/W/O emulsions prepared by either the ultrasonic vibrator or the mechanical homogenizer, the two-phase W/O emulsions appeared to have a lower fuel consumption rate, bsfc, CO, and a lower black smoke opacity than the three-phase O/W/O emulsions, regardless of whether they were prepared by ultrasonic vibrator or mechanical homogenizer.     

Engine performance and emission characteristics of a three-phase emulsion of biodiesel produced by peroxidation

Biodiesel, which is produced from vegetable oils, animal fats or used cooking oils, can be used as an alternative fuel for diesel engines. The high oxygen content of biodiesel not only enhances its burning efficiency, but also generally promotes the formation of more nitrogen oxides (NO_x) during the burning process. Fuel emulsification and the use of NO_x inhibitor agents in fuel are considered to be effective in reducing NO_x emissions. In the study reported herein, soybean oil was used as raw oil to produce biodiesel by transesterification reaction accompanied by peroxidation to further improve the fuel properties of the biodiesel, which was water washed and distilled to remove un-reacted methanol, water, and other impurities. The biodiesel product was then emulsified with distilled water and emulsifying surfactant by a high-speed mechanical homogenizer to produce a three-phase oil-droplets-in-water-droplets-in-oil (i.e. O/W/O) biodiesel emulsion and an O/W/O emulsion that contained aqueous ammonia, which is a NO_x inhibitor agent. A four-stroke diesel engine, in combination with an eddy-current dynamometer, was used to investigate the engine performance and emission characteristics of the biodiesel, the O/W/O biodiesel emulsion, the O/W/O biodiesel emulsion that contained aqueous ammonia, and ASTM No. 2D diesel. The experimental results show that the O/W/O emulsion has the lowest carbon dioxide (CO₂) emissions, exhaust gas temperature, and heating value, and the largest brake specific fuel consumption, fuel consumption rate, and kinematic viscosity of the four tested fuels. The increase of engine speed causes the increase of equivalence ratio, exhaust gas temperature, CO₂ emissions, fuel consumption rate, and brake specific fuel consumption, but a decrease of NO_x emissions. Moreover, the existence of aqueous ammonia in the O/W/O biodiesel emulsion curtails NO_x formation, thus resulting in the lowest NO_x emissions among the four tested fuels in burning the O/W/O biodiesel emulsion that contained aqueous ammonia.     

Engine performance and emission characteristics of three-phase diesel emulsions prepared by an ultrasonic emulsification method

The emulsification method is a potential technique for reducing pollutant emissions from combustion equipment primarily due to occurrence of micro-explosion to enhance burning. In this study, an ultrasonic emulsification method was applied to prepare two-phase water-in-oil (W/O) and three-phase oil-in-water-in-oil (O/W/O) emulsions. The engine performance and the pollutant emission characteristics of a diesel engine were measured and analyzed. A rather violent ultrasonic wave may result in the phenomena of cavitations and hot spots, which in turn promotes fast chemical and physical reactions. Various kinds of liquid, which are immiscible with each other, may thus become highly mixed so that an emulsion is formed. This study first used an ultrasonic oscillating bath to produce ultrasonic waves by which two- and three-phase emulsions were prepared. The experimental results show that the emulsions prepared by the ultrasonic vibrating method have much finer and better-distributed droplets. The use of these emulsions as an engine fuel produced lower NO emission, lower soot concentration and lower black smoke opacity, while creating a larger brake specific fuel consumption (bsfc) and a larger CO emission compared with that of an engine using neat diesel fuel. However, the variations in the concentrations of CO₂ and O₂ emissions between the emulsions and neat diesel fuel were not significant. In a comparison with the characteristics of the two-phase W/O emulsion, the three-phase O/W/O emulsion was found to have a larger CO emission, larger soot particles and larger bsfc while producing a lower brake thermal efficiency and a lower black smoke opacity.     

De-emulsification of 2-ethyl-1-hexanol/water emulsion using oil-wet narrow channel combined with low-speed rotation

Low-speed rotation of disc in an internal circulation of a novel de-emulsification with rotation-dise horizental contactor (RHC-D) realized de-emulsification for O/W emulsions due to repeated coalescence in oil-wet narrow channels at a low rotation speed. For three emulsions included ethanol/water/2-ethyl-1-hexanol, ethanol/water/2-ethyl-1-hexanol/SDS (Sodium Dodecyl Sulfonate) and 2-ethyl-1-hexanol/water/SDS emulsion, deemulsification ratios of oil phase could reach 1, 1 and 0.67 respectively at 170 r·min^-1, and de-emulsification ratios increased obviously after agitating 10 min. De-emulsification experiment in the seam indicated that oil droplet sizes in O/W emulsion became larger after de-emulsification. The main de-emulsification mechanism in RHCD was the coalescence of oil droplets in oil-wet narrow channels. With increase of the rotation speed, oil droplets dispersed better in the aqueous phase. However, de-emulsification effect enhanced due to the increase of the coalescence rate at a bit higher rotation speed. In addition, internal circulation made those O/W emulsions to be broken repeatedly, consequently de-emulsification ratio increased. Repeated de-emulsification through internal circulation might make continuous extraction of ethanol come true at a low rotation speed.     

三元复合驱中原油乳化作用研究

通过乳状液稳定实验考察了大庆油田碱-表面活性剂-聚合物三元复合驱过程乳状液的形成机理、乳状液类型及稳定性。结果表明,大庆原油与碱反应1d时,测得其浓相体积分数为25%,所形成的乳状液为O/W型乳状液,而随着原油与碱作用时间的增加,其浓相体积分数达到40%以上,形成W/O型乳状液,且乳状液稳定性随作用时间增加而增强。大庆原油与水溶性表面活性剂ORS-41溶液作用时,所形成的乳状液为O/W型,且乳状液的稳定性与原油和ORS-41作用时间的长短关系较小。原油与NaOH和ORS-41混合溶液作用时,形成上层为W/O型乳状液,下层为O/W型乳状液的混合体系。     

Characterization of a double emulsion system (oil-in-water-in-oil emulsion) with low solid fats: Microstructure

A double emulsion system [oil-in-water-in-oil (O/W/O)] with 16.3% (w/w) water and 83% (w/w) oil was prepared and stabilized using a novel method of mixing two oil-in-water (O/W) emulsions together. The first emulsion consisted of 85% (w/w) liquid canola oil, 14.4%(w/w) water, 0.5% (w/w) sodium caseinate, and 0.1% (w/w) lecithin and the second emulsion contained 73% (w/w) canola oil, 8% (w/w) palm-cotton stearin (50∶50), 0.2% (w/w) lecithin, 18.2% (w/w) water, and 0.6% (w/w) sodium caseinate. Mixing the two emulsions (50∶50) by weight produced a product with 79% (w/w) liquid canola oil and 4% (w/w) palm-cotton stearin. The two O/W emulsions were prepared separately at 50°C, mixed together at 45°C for 2–5 min, and then supercooled in a −5°C ice/salt bath while mixing at low shear rates (2,000–3,000 rpm). Under supercooling conditions the fat globules in the second emulsion (containing liquid oil and stearin) began to break down as a result of fat crystal growth and shearing action and release plastic fat. During this stage, the continuous aqueous phase underwent a phase transition and the emulsion viscosity dropped from 37,000–50,000 to 250 cP. The released plastic fat continued to harden as the temperature dropped and stabilized the first O/W emulsion (containing only liquid oil). The low shear rate mixing was stopped when the temperature dropped below 15°C and before the O/W/O emulsion hardens. Microstructural analysis of the first emulsion before and after supercooling showed essentially intact fat globules. The microstructure of the second emulsion before supercooling showed the same intact globules as the first emulsion, but after supercooling, an amorphous mass with only a few intact globules was seen. By mixing the two emulsions together and supercooling, a stable O/W/O emulsion was formed with plastic fat as the continuous phase and the first O/W emulsion as the dispersed phase.     

Efficient Encapsulation of a Water-Soluble Molecule into Lipid Vesicles Using W/O/W Multiple Emulsions via Solvent Evaporation

We developed a novel method for preparing lipid vesicles with high entrapment efficiency and controlled size using water‐in‐oil‐in‐water (W/O/W) multiple emulsions as vesicle templates. Preparation consists of three steps. First, a water‐in‐oil (W/O) emulsion containing to‐be‐entrapped hydrophilic molecules in the water phase and vesicle‐forming lipids in the oil phase was formulated by sonication. Second, this W/O emulsion was introduced into a microchannel emulsification device to prepare a W/O/W multiple emulsion. In this step, sodium caseinate was used as the external emulsifier. Finally, organic solvent in the oil phase was removed by simple evaporation under ambient conditions to afford lipid vesicles. The diameter of the prepared vesicles reflected the water droplet size of the primary W/O emulsions, indicating that vesicle size could be controlled by the primary W/O emulsification process. Furthermore, high entrapment yields for hydrophilic molecules (exceeding 80 % for calcein) were obtained. The resulting vesicles had a multilamellar vesicular structure, as confirmed by transmission electron microscopy.     

Crystallization Enhancement by a High Behenic Acid Stabilizer in a Palm Oil-Based Model Fat Blend and its Corresponding Fat-Reduced Water-in-Oil Emulsion

A high behenic stabilizer (HBS) at concentrations of 0.3%, 0.6%, and 0.9% w/w was added to the oil phase of a fat-reduced water-in-oil (W/O) emulsion intended for margarine manufacture. The crystallization kinetics, thermal behavior, and microstructure of an oil phase and its 35/65 w/w fat-reduced W/O emulsion were studied. The oil phase was composed of a palm oil-based model fat blend, three emulsifiers, and the HBS. Differential scanning calorimetry results showed that, when 0.9% of stabilizer was added, the crystallization started 2.5 °C higher than when no HBS was added, hence reducing the time needed for crystallization. Polarized light microscopy results showed that the cocrystallization of the high-melting triacylglycerols of the oil phase with the HBS significantly decreased the fat crystal size and increased the number of crystals. The solid fat content also was increased by 2.4%. Interfacial tension experiments corroborated that HBS was located in the oil phase and not at the emulsion interface. This work shows that margarine can be successfully manufactured by adding 0.9% HBS to a 35/65 w/w fat-reduced W/O emulsion without losing functionality, as shown by the presence of the β′ polymorph. This work also suggests that 15% fat could be removed from the system without changing functionality by merely adding up to 0.9% of HBS.