The Applicability of Inverse Water-in-oil Emulsion as a Selective Plugging Agent

The presence of homogeneous porous media allows a uniform sweep during a waterflooding process, but it is very rare to find homogeneous reservoirs. The typical heterogeneous character of most formations causes an uneven production from different permeability sands in the reservoir. The preferential movement of the injected water to zones with less resistance to flow causes earlier water breakthrough time than if the formation was homogeneous. This phenomenon will exacerbate at offshore reservoirs and the wells with water production potential. To suggest a solution to this problem, the use of emulsions as a mobility control and selective plugging agent has been studied here. Three different W/O emulsion formulations were injected into high-permeable heavy oil saturated waterflooded sandpacks and the one with the best recovery factor was injected to sandpacks with different permeabilities. The change in oil recovery pattern is considered as the main aim of this work. Experiment results revealed that invert W/O emulsions with high viscosities could act as a selective plugging agent and help the displacement process.     

非牛顿稠油包水乳状液的剪切稀释性

以现场稠油和矿化水为工质,制备了多组不同微观液滴分布的W/O型乳状液,结合显微镜观察及测量分析,获得了对稠油包水乳状液微观液滴分布及非牛顿性的定量分析。结果表明,随微观液滴直径的减小,乳状液体系将具有更高的表观黏度,并表现出更强的剪切稀释性;结合颗粒雷诺数（η_r-N_Re,p 关系）,能够很好的表征剪切率及微观液滴分布对稠油包水乳状液剪切稀释性的共同影响。     

Experimental investigation of the effects of various parameters on viscosity reduction of heavy crude by oil–water emulsion

The effects of water content, shear rate, temperature, and solid particle concentration on viscosity reduction(VR) caused by forming stable emulsions were investigated using Omani heavy crude oil. The viscosity of the crude oil was initially measured with respect to shear rates at different temperatures from 20 to 70 C. The crude oil exhibited a shear thinning behavior at all the temperatures. The strongest shear thinning was observed at 20 C. A non-ionic water soluble surfactant(Triton X-100) was used to form and stabilize crude oil emulsions. The emulsification process has significantly reduced the crude oil viscosity. The degree of VR was found to increase with an increase in water content and reach its maximum value at 50 % water content.The phase inversion from oil-in-water emulsion to water-inoil emulsion occurred at 30 % water content. The results indicated that the VR was inversely proportional to temperature and concentration of silica nanoparticles. For water-in-oil emulsions, VR increased with shear rate and eventually reached a plateau at a shear rate of around350 s-1. This was attributed to the thinning behavior of the continuous phase. The VR of oil-in-water emulsions remained almost constant as the shear rate increased due to the Newtonian behavior of water, the continuous phase.     

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.     

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%。     

EFFECT OF ASPHALTENE AND RESINS ON THE STABILITY OF WATER-IN-WAXY OIL EMULSIONS

Asphaltene, resins and paraffin waxes, their mutual interactions and their influence on the stability of water-in-oil emulsions have been studied. 20 wt % paraffin wax dissolved in decalin was used to model the waxy crude oil. Asphaltene and resins separated from a crude oil were used to stabilize the water-in-oil emulsions. Synthetic formation water was utilized as the aqueous phase of the emulsion. The emulsion stability increased with increasing the concentration of asphaltene with a subsequent decrease in the average particle size distribution of the emulsion. Resins alone are not capable of stabilizing the emulsion, however, in the presence of asphaltene they form very stable emulsions. Dynamic viscosity and pour point measurements provided evidence for resins-paraffin waxes interactions. Asphaltene in the form of solid aggregates form suitable nuclei for the wax crystallites to build over with a mechanism similar to that of paraffin wax crystal-modifiers. As asphaltene are polar in nature they are derived at the oil/water interface which was proved by the ability of asphaltene to reduce oil/water interfacial tension. Consequently, nucleation of the wax crystallites by asphaltene and resins at the interface will add to the thickness of the oil-water interfacial film and hence increase the stability of the emulsion.     

基于乳状液转相技术的钻井液新体系室内研究

为有效解决油基钻井液应用中存在的固井质量较差、环境污染严重等问题,采用有机胺质子化可逆原理,赋予油基钻井液以乳化相态的可逆性,研制了一套可逆乳化钻井液体系。该钻井液体系的配方为5#白油+25.0%CaCl2溶液+1.0%有机土+0.5%石灰+1.0%润湿剂RS+4.0%乳化剂ET,油水比为50:50,密度为1.2 kg/L。通过室内试验对该钻井液体系进行了全面的性能评价,结果表明,通过酸触相反转和碱触相回转,可实现W/O型与O/W型间自由转换;且转换前后的钻井液性能良好:破乳电压达500~900 V,抗温达180 ℃,高温高压滤失量小于15 mL,流变性与传统逆乳化钻井液相当,可抗10%硫酸钙、20%钻屑污染,渗透率恢复率和滚动回收率都达90%以上,泥饼和含油钻屑更易处理。这说明,研制的可逆乳化钻井液体系兼备油基钻井液和水基钻井液的优点,且各项性能均为优良,能解决常规油基钻井液应用中存在的问题。      

EFFECT OF ASPHALTENE AND RESINS ON THE STABILITY OF WATER-IN-WAXY OIL EMULSIONS

ABSTRACT

Asphaltene, resins and paraffin waxes, their mutual interactions and their influence on the stability of water-in-oil emulsions have been studied. 20 wt % paraffin wax dissolved in decalin was used to model the waxy crude oil. Asphaltene and resins separated from a crude oil were used to stabilize the water-in-oil emulsions. Synthetic formation water was utilized as the aqueous phase of the emulsion. The emulsion stability increased with increasing the concentration of asphaltene with a subsequent decrease in the average particle size distribution of the emulsion. Resins alone are not capable of stabilizing the emulsion, however, in the presence of asphaltene they form very stable emulsions. Dynamic viscosity and pour point measurements provided evidence for resins-paraffin waxes interactions. Asphaltene in the form of solid aggregates form suitable nuclei for the wax crystallites to build over with a mechanism similar to that of paraffin wax crystal-modifiers. As asphaltene are polar in nature they are derived at the oil/water interface which was proved by the ability of asphaltene to reduce oil/water interfacial tension. Consequently, nucleation of the wax crystallites by asphaltene and resins at the interface will add to the thickness of the oil-water interfacial film and hence increase the stability of the emulsion.     

Stability of Water-in-Crude Oil Emulsions: Effect of Oil Aromaticity,Resins to Asphaltene Ratio,and pH of Water

Abstract

The formation of tight water-in-oil emulsions during production and transport of crude oils is a great problem challenging the petroleum industry. Tremendous research works are directed to understanding the mechanism of formation, stabilization, and controlling of oil field emulsions. This article presents experimental results of some of the factors controlling the formation and stabilization of water-in-crude oil emulsions. In this study, asphaltenes and resins separated from emulsion samples collected from Burgan oil field in Kuwait have been used to study emulsion stability. Model oils of resin to asphaltene ratio of 5:1 and toluene-heptane mixtures have been used to study the effect of oil aromaticity on emulsion stability. Results indicate that at low toluene content (below 20%) or high content (above 40%) less stable emulsions are formed. At a threshold value of 30% toluene, a very tight model oil emulsion is formed. The effect of resins to asphaltene (R/A) ratio on stability of model oil has also been investigated. Results reported in this paper show that as the R/A increases the emulsions become less stable. The effect of pH on stability of model oil emulsion made of 50/50 heptane-toluene mixture having R/A ratio of 5:1 have been studied. Experimental results revealed that as the pH of the aqueous phase of model oil increased from 2 to 10, the emulsion became less stable. At high pH, the asphaltene particles are subjected to complete ionization leading to destruction of the water-oil interface and eventually breakdown of the emulsion.     

Viscosity Reduction of Heavy and Extra Heavy Crude Oils by Pulsed Electric Field

Abstract

The ever-increasing world energy demand would require the use of all hydrocarbon resources available, especially heavy and extra-heavy crude oils in the near future. However, transportation of these crudes is very difficult due to their high viscosity and low mobility. There are many different methods to reduce heavy crude oil viscosity. Some of these methods are heating, blending, water-in-oil emulsion formation, upgrading, and core annular flow. But each of these methods has several problems. The aim of this research is to investigate a new method to reduce viscosity for pipeline transportation. In this method asphalt molecules, which are mainly responsible for high viscosity, are aggregated temporarily to micronized clusters while going through a pulsed electric field, causing a reduction of the viscosity. This method does not change the oil's temperature and is very suitable for underwater pipelines. The authors applied electric fields in the range of 0.5 to 1.8 KV/mm an Iranian heavy crude oil and viscosity reduction up to 7% was observed.     

The Viscosity Reduction of Heavy and Extra Heavy Crude Oils by a Pulsed Magnetic Field

Abstract

Ever increasing world energy demand requires the use of all hydrocarbon resources available, especially heavy and extra heavy crude oils, in the near future. However, transportation of these crudes is very difficult due to their high viscosity and low mobility. There are many different methods to reduce heavy crude oil viscosity. Some of these methods are heating, blending, water-in-oil emulsion formation, upgrading, and core annular flow, but each of these methods has several problems. The aim of this research is to investigate a new method to reduce viscosity for pipeline transportation. In this method, asphalt molecules, which are mainly responsible for high viscosity, are aggregated temporarily to micronized clusters while going through a pulsed electric field, causing a reduction of the viscosity. This method does not change the oil's temperature and is very suitable for underwater pipelines. Magnetic fields of 0.03 to 0.3 T were exerted on two kinds of heavy crude oils and viscosity reduction up to 7% was observed.     

抗高温油基钻井液主乳化剂的合成与评价

以妥尔油脂肪酸和马来酸酐为主要原料合成了一种油基钻井液抗高温主乳化剂HT-MUL,并确定了妥尔油脂肪酸单体的最佳酸值及马来酸酐单体的最优加量。对HT-MUL进行了单剂评价,结果表明HT-MUL的乳化能力良好,配制的油水比为60:40的油包水乳液的破乳电压最高可达490 V,90:10的乳液破乳电压最高可达1000 V。从抗温性、滤失性、乳化率方面对HT-MUL和国内外同类产品进行了对比,结果表明HT-MUL配制的乳液破乳电压更大、滤失量更小、乳化率更高,整体性能优于国内外同类产品。应用主乳化剂HT-MUL配制了高密度的油基钻井液,其性能评价表明体系的基本性能良好,在220℃高温热滚后、破乳电压高达800 V,滤失量低于5 mL。HT-MUL配制的油基钻井液具有良好的抗高温性和乳化稳定性。      

Effect of asphaltene,carbonate, and clay mineral contents on water cut determination in water–oil emulsions

The role of asphaltene, carbonate, and clay contents on the stability of water–oil emulsions and water cut determination was evaluated via both IR analysis and physicochemical properties of the tested mixtures. To study the effect of asphaltene addition, 10 emulsions were prepared. The first five emulsions contained different water cuts from 10 to 50 wt.%, and constant asphaltene ratio of 0.2 wt.% while the second five specimens contained different asphaltene ratios of 0.1, 0.3, 0.5, and 0.7 wt.%.To study the effect of clay types, 10 water-in-oil emulsions with different clay types (kaolinite and bentonite) and different water cuts from 10–50 wt.% were tested. To study the effect of clay ratios, six water-in-oil emulsions with different clay types and ratios of 2, 4, and 8 wt.% were prepared. The effect of carbonate type was studied with the use of calcite (CaCO₃), magnesite (MgCO₃), and dolomite (CaMg (CO₃)₂), and different water cuts from 10–50 wt.% The effect of different carbonate ratios of 1, 3, and 5 wt.% was also studied.Relationships between water cut, major functional groups, and mixture physicochemical properties were developed. Therefore, for a known property, water cut could be predicted.     

大庆西部斜坡稠油地层流动性影响因素实验研究

针对大庆西部斜坡稠油在开采过程中与地层水和注入水乳化生成高黏的油包水型乳状液降低地层流动性的问题,通过流变性实验和岩心流动实验,研究了乳化、温度及地层渗透率对稠油黏度和地层流动性的影响规律,明确了原油在地层中流动困难的原因及改善流动性的技术方向。结果表明：含水乳化和温度是影响其黏度的主要因素,温度由30℃上升至120℃,脱水稠油黏度降低了95.5%;当含水率低于70%时,原油与水形成油包水型乳状液,含水率越大黏度越大,含水率为70%的稠油的黏度是脱水黏度的30倍左右;地层渗透率、温度及含水乳化对原油地层流动性具有显著的影响,地层渗透率越低、温度越低、含水乳化越严重,原油流动性越差,不同温度和含水率下的采油指数相差可达10倍以上。因此,促使含水稠油乳状液转相是油田降黏增产的有效途径。研究成果对同类油藏开发具有重要的指导意义。      

MINERAL MATTER AND CLAY-ORGANIC COMPLEXES IN OIL SANDS EXTRACTION PROCESSES

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the bitumen product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed.

The samples were obtained from Suncor's oil sands extraction plant located in Fort McMurray, Alberta. Samples were obtained from throughout the extraction process from the primary froth through to the final diluted bitumen product. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as well as with other techniques such as interfacial tension measurements. The data indicates that high water content products originate, to a great extent, from the presence of a very hydrophilic organic matrix attached to the surface of the clay and heavy metal minerals.     

Viscosity of Concentrated Emulsions: Relative Effect of Granulometry and Multiphase Morphology

Abstract

High viscosity and high density make heavy and extra heavy crude oils very difficult to produce. They cannot be pumped in their natural state and advanced technologies are required. Formation of oil-in-water emulsions is one of them. A typical emulsion contains 65% of dispersed phase and has a viscosity lower than 500 mPa.s. Current research is aimed at increasing the crude oil content at reduced costs with still good stability and low viscosity. Consequently, an experimental study was dedicated to the relationship between the structure and the rheological properties of heavy oil emulsions. Particular attention was paid to process parameters employed to prepare emulsions. Depending on the shear device, various emulsions have been obtained, either simple or multiple, monodisperse or bimodal. The resulting viscosity is discussed. It is particularly low when the emulsion is either coarse and unimodal or fine and simple. The highest viscosity is obtained when the emulsion is fine and multiple. The experimental results confirm that both composition variables and process parameters have to be taken into account to minimize viscosity of heavy oil emulsions.     

水包稠油乳状液中孤岛稠油组分间相互作用初探

 研究了孤岛稠油脱沥青质油、胶质、沥青质及胶质与沥青质混合物对水包稠油乳状液界面性质的影响。结果表明，具有高芳碳率、低烷基碳率、高芳香环缩合程度的沥青质组分界面活性较高。在水包稠油乳状液形成过程中，芳香分的存在有利于以稠合芳香环系为核心的胶质粒子的溶解，促进胶质单元结构在油滴表面的吸附，使脱沥青质油的界面活性高于胶质。胶质对沥青质有很好的分散作用，使沥青质在油相中溶解度增加，沥青质分子以较小的缔合体或以自由分子状态存在，沥青质分子中所有极性基团较易到达表面上，使油水界面张力降低。稠油组分与阴离子乳化剂LAS存在正的协同作用，与非离子乳化剂OP-10存在负的协同作用。稠油各组分共同与乳化剂作用形成稳定的水包稠油乳状液。     

MINERAL MATTER AND CLAY-ORGANIC COMPLEXES IN OIL SANDS EXTRACTION PROCESSES

ABSTRACT

Differences in oil sands processability and extraction yields can be dependent upon many factors including the composition of the mineral components and the organic complexes that are associated with certain minerals. These mineral-organic associations help provide the bridge which leads to carry over of bitumen with the tailings as well as carry over of water and mineral matter with the bitumen product. The nature of the organic component of clay-organic complexes extracted from various streams in an oil sands recovery process is discussed in relation to the stability of both water-in-oil and oil-in-water emulsions formed.

The samples were obtained from Suncor's oil sands extraction plant located in Fort McMurray, Alberta. Samples were obtained from throughout the extraction process from the primary froth through to the final diluted bitumen product. These samples have been studied with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) as well as with other techniques such as interfacial tension measurements. The data indicates that high water content products originate, to a great extent, from the presence of a very hydrophilic organic matrix attached to the surface of the clay and heavy metal minerals.     

VISCOSITY OF WATER-OIL EMULSIONS WITH ADDED NANO-SIZE PARTICLES

The viscosity of emulsion and suspensions in the presence of two types of nano-size particles that, have different affinity for oil, have been investigated. It has been found out that both oil-solid suspensions and oil-water-solid mixtures behave as pseudoplastic fluids at all studied solid concentrations. The viscosity of emulsion-solid mixtures does not seem to get affected by water concentration, yet it is a function of solid concentration.

The ability of solids to act as emulsifying agents has also been investigated. It has been established that neither of the two types of solids used is capable of stabilizing water-in-oil or oil-in-water emulsions in the absence of surfactants. At low concentrations of solids and in the presence of an oil-soluble surfactant, both oil-wet and water-wet solids, however, are capable of stabilizing water-in-oil emulsions. In the presence of water-soluble surfactant, only water-wet solids are capable of stabilizing oil-in-water emulsions.