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.     

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.     

Characterization of Asphaltenes and Resins Separated from Water-in-Oil Emulsions

Knowledge of the properties and behavior of asphaltenes and resins is indispensable for the design of preventive and curative measure for emulsion problems created by the presence of asphaltene, resins, and other organic and inorganic solids. In order to understand the phenomena of water-oil emulsions formed in Kuwaiti oil fields and determine the factors involved in the stabilization of these emulsions, the role of asphaltenes, resins and wax separated from various samples of oil field emulsions formed in Burgan oil field have been evaluated. Physicochemical properties of asphaltenes, resins, wax, and de-asphalted de-resined (DADR) oil samples have been studied via FT-IR, ¹H, and ¹³C NMR, elemental analysis, and differential scanning calorimetry (DSC). These emulsion samples contain different amounts of water ranges from 24 to 35%, asphaltene content ranges from 0.9 to 1.7%, and resin content from 3.7 to 4.6%. IR-FT spectra were performed to identify the various functional groups which have an effect on the stability of water-oil emulsions. The freezing behavior of an emulsion was characterized by differential scanning calorimetry to determine whether the water in the emulsion is free water or emulsified water.     

Characterization of Asphaltenes and Resins Separated from Water-in-Oil Emulsions

Abstract

Knowledge of the properties and behavior of asphaltenes and resins is indispensable for the design of preventive and curative measure for emulsion problems created by the presence of asphaltene, resins, and other organic and inorganic solids. In order to understand the phenomena of water-oil emulsions formed in Kuwaiti oil fields and determine the factors involved in the stabilization of these emulsions, the role of asphaltenes, resins and wax separated from various samples of oil field emulsions formed in Burgan oil field have been evaluated. Physicochemical properties of asphaltenes, resins, wax, and de-asphalted de-resined (DADR) oil samples have been studied via FT-IR, ¹H, and ¹³C NMR, elemental analysis, and differential scanning calorimetry (DSC). These emulsion samples contain different amounts of water ranges from 24 to 35%, asphaltene content ranges from 0.9 to 1.7%, and resin content from 3.7 to 4.6%. IR-FT spectra were performed to identify the various functional groups which have an effect on the stability of water-oil emulsions. The freezing behavior of an emulsion was characterized by differential scanning calorimetry to determine whether the water in the emulsion is free water or emulsified water.     

RHEOLOGY,PARTICLE SIZE DISTRIBUTION,AND ASPHALTENE DEPOSITION OF VISCOUS ASPHALTIC CRUDE OIL-IN-WATER EMULSIONS FOR PIPELINE TRANSPORTATION

The rheology of an asphaltic heavy crude oil-in-water emulsions stabilized by an anionic (RN) and a nonionic (TEP) surfactants individually or in a mixture has been studied. The investigated crude oil has a non-Newtonian, time dependent, shear thickening, rheopectic behavior with a relatively high yield stress. The relatively high yield stress of this crude oil is attributed to the presence of a relatively high asphaltene and resins content. The viscosity ofhe crude oil decreases when it is emulsified with synthetic formation water in the form of an oil-in-water type of emulsion using a nonionic or an anionic surfactant. It has been found that, the maximum oil content required for forming an oil-in-water emulsion of acceptable viscosity is the 60% oil-containing emulsion. However, the 70% oil-containing emulsion is not an oil-in-water type of emulsion but it is rather a complicated mixture of oil-in-water-in-oil type of emulsion. The presence of the anionic and the nonionic surfactants together has a synergistic effect in decreasing the total surfactant concentration required to stabilize the emulsion and to form low viscosity emulsion. It has been emphasized that the nonionic surfactant has a positive contribution in forming emulsions with low viscosity. Meanwhile, the anionic surfactant contributes in stabilizing the emulsion at lower concentrations. Flocculation point measurements showed that the added surfactants caused no sign of asphaltene deposition. This implies that it is safe to use the investigated surfactants in forming oil-in-water emulsion for viscous asphaltic crude oils without any fear of asphaltene deposition.     

RHEOLOGY, PARTICLE SIZE DISTRIBUTION, AND ASPHALTENE DEPOSITION OF VISCOUS ASPHALTIC CRUDE OIL-IN-WATER EMULSIONS FOR PIPELINE TRANSPORTATION

The rheology of an asphaltic heavy crude oil-in-water emulsions stabilized by an anionic (RN) and a nonionic (TEP) surfactants individually or in a mixture has been studied. The investigated crude oil has a non-Newtonian, time dependent, shear thickening, rheopectic behavior with a relatively high yield stress. The relatively high yield stress of this crude oil is attributed to the presence of a relatively high asphaltene and resins content. The viscosity ofhe crude oil decreases when it is emulsified with synthetic formation water in the form of an oil-in-water type of emulsion using a nonionic or an anionic surfactant. It has been found that, the maximum oil content required for forming an oil-in-water emulsion of acceptable viscosity is the 60% oil-containing emulsion. However, the 70% oil-containing emulsion is not an oil-in-water type of emulsion but it is rather a complicated mixture of oil-in-water-in-oil type of emulsion. The presence of the anionic and the nonionic surfactants together has a synergistic effect in decreasing the total surfactant concentration required to stabilize the emulsion and to form low viscosity emulsion. It has been emphasized that the nonionic surfactant has a positive contribution in forming emulsions with low viscosity. Meanwhile, the anionic surfactant contributes in stabilizing the emulsion at lower concentrations. Flocculation point measurements showed that the added surfactants caused no sign of asphaltene deposition. This implies that it is safe to use the investigated surfactants in forming oil-in-water emulsion for viscous asphaltic crude oils without any fear of asphaltene deposition.     

油包水乳状液中胶质和沥青质的界面剪切黏度和乳状液稳定性的关系

 采用红外和紫外光谱分析了胜利原油中胶质和沥青质的结构，采用界面剪切黏度对其油、水界面膜强度进行了表征，测定了胶质和沥青质模拟油油包水乳状液的稳定性。结果表明，沥青质和胶质的结构和相对分子质量不同，沥青质含有更多的芳环结构，相对分子质量比胶质大，界面膜强度也比胶质强，其乳状液更稳定。     

原油乳状液稳定性研究 Ⅱ.原油成分对原油乳状液稳定性的影响

原血成分的表面活性物质及其细微固体颗粒,在油水界面上相互作用是原油乳状液其有稳定性的主要原因。本文采用简单的方法将原油中众多的物质分成两大类,并根椐它们单独时或混合后对癸烷/水乳状液稳定性作用的特征,将其分别称为原油乳化剂和原油破乳剂。试验表明,原油乳状液稳定性的高低主要取决于所含的这两大类物质的多少和相对比例,其相对重要性可由界面张力定性地反映出来;并且由原油/水界面张力的大小可以定性地评估原油乳状液的稳定性。     

长庆油包水乳状液的稳定性与沥青质含量的关系

以长庆轻质原油为例,探讨了原油组分对乳状液稳定性的影响规律;采用煤油萃取轻质组分及二 甲苯溶解沥青质两种方法证实了沥青质是稳定轻质油包水乳状液的主要因素;采用流变仪、布氏黏度计 和光学显微镜等仪器测定了含水原油乳状液界面膜强度、油相黏度和乳状液尺寸。结果表明,取决于沥 青质的油 水界面膜强度和油相黏度是影响原油乳状液稳定性的主要因素,沥青质含量越高,油 水界 面膜强度和油相黏度越大,乳状液越稳定。     

原油复配破乳剂的配方设计

研究了水相pH值、非离子破乳剂和助剂对沙轻原油、阿曼原油、杰诺原油、胜利原油乳液稳定性的影响 ,考察了破乳剂与助剂的协同效应。结果表明 :沙轻原油在水相 pH =6～ 7时乳液的稳定性最差 ;破乳剂通过降低界面张力和使沥青质胶团向油相解缔而破坏乳液的稳定性 ;有机小分子助剂改变界面极性环境或增加芳香度使沥青质增溶而破坏乳液的稳定性 ,它们与破乳剂有很好的协同效应     

Effect of oxyethylated isononylphenol (neonol) on viscosity characteristics of water–oil emulsions

The effect of oxyethylated isononylphenol (AF 9-10 neonol) on the rheology of natural water–oil emulsions has been investigated. It was determined that paraffins and asphaltenes play an important role in the stabilization of water–oil emulsion and their structure formation. Addition of AF 9-10 neonol to the water–oil emulsion leads to a significant decrease in its viscosity, which is particularly strong in the case of the oil emulsions with high asphaltene and resin contents. It was determined that, with the addition of 3% neonol to the water–oil emulsion, a decrease in viscosity is maximum.     

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.     

STABILITY AND RHEOLOGY OF HEAVY CRUDE OIL-IN-WATER EMULSION STABILIZED BY AN ANIONIC- NONIONIC SURFACTANT MIXTURE

The stability and rheology of an Egyptian Heavy crude oil-in-water emulsions stabilized by an anionic (TDS) and a nonionic (NPE) surfactants individually or in a mixture have been studied. The study reveals that, the viscosity of the crude oil decreases when it is emulsified with water in the form of an oil-in-water type of emulsion. The stability of the oil-in-water emulsion increases as the surfactant concentration and speed of mixing of the emulsion increases. Fresh water and synthetic formation water have been used to study the effect of aqueous phase salinity on the stability and viscosity of the emulsion. Surfactant dissolved in synthetic formation water has been utilized to find out the possibility of injecting the surfactant into a well bore to effect emulsification in the pump or tubing for enhancing the production of heavy crude oils as oil-in-water emulsion. The study revealed that, the viscosity of the emulsion containing fresh water is always less than that containing formation water, these findings have been correlated with the crude oil/water interracial tension (IFT) measurements The decreased IFT value results in a decrease in the average particle size of the dispersed crude oil leading     

影响塔河油田酸化油破乳的因素分析

酸化油破乳一直是困扰油田的技术难题,采用光散射法及静电场法研究了塔河油田的2种酸化油破乳情况,然后从残余药剂、固体颗粒、胶质与沥青质3方面分析了影响酸化油破乳的主要原因。结果表明：压裂液中的瓜胶及酸化液中的盐酸不利于破乳;固体颗粒主要为亲油型硫铁类化合物,促进W/O采出液的稳定;酸化油中沥青质聚集体的溶解性更差,易于形成稳定的沥青质膜。上述3种因素的协同作用导致酸化油破乳难度加大。     

原油乳状液油-水界面上活性物的结构和活性

通过综合的方法分离出大庆原油和胜利原油乳状液油-水界面上的活性物，用元素分析、红外、核磁、色质联用等方法分析其化学结构，并在油饿水模型体系中测定了它们的动态界面张力，考察其化学结构与界面活性之间的关系。结果表明，水相的pH值影响原油中的含氧化合物在油．水界面膜上的吸附；沥青、胶质和蜡是界面活性物的主要成分，对油-水界面膜的形成和稳定起着重要的作用；原油的酸性组分对油-水界面膜的动态界面张力有着决定性的影响。     

原油正构烷烃沥青质聚沉机理研究及沉淀量测定

用IP 143标准方法测定了我国孤岛和草桥原油正构烷沥青质沉淀量。结果表明两种原油的沥青质沉淀量均随沉淀剂分子量增大而减小、随剂油比增大而增大。在原油沥青质 胶质胶束模型的基础上提出了一种新的沥青质聚沉机理 ,该机理的基本假设是原油中沥青质分子以胶束形式存在 ,其中胶核为沥青质缔合物 ,溶剂化层为胶质和溶剂分子。通过分析沉淀剂性质、剂油比、体系温度和压力等对沥青质 胶质胶束稳定性的影响得出了沥青质沉淀点、沉淀量、沉淀物平均分子量以及沉淀物平均颗粒大小随沉淀剂性质和剂油比等因素变化的规律。经比较说明 ,这些规律与本文及文献实验结果相符     

PETROLEUM RESINS: SEPARATION, CHARACTER, AND ROLE IN PETROLEUM

In petroleum science, the term resin generally implies material that has been eluted from various solid adsorbents, whereas the term maltenes (or petrolenes) indicates a mixture of the resins and oils obtained as filtrates from the asphaltene precipitation. Thus, after the asphaltenes are precipitated, adsorbents are added to the n-pentane solutions of the resins and oils, by which process the resins are adsorbed and subsequently recovered by the use of a more polar solvent, and the oils remain in solution. The resin fraction plays an important role in the stability of petroleum and prevents separation of the asphaltene constituents as a separate phase. Indeed, the absence of the resin fraction (produced by a variety of methods) from the maltenes influences the ability of the de-resined maltenes to accommodate the asphaltenes either in solution or as a stable part of a colloidal system. In spite of the fact that the resin fraction is extremely important to the stability of petroleum, there is surprisingly little work reported on the characteristics of the resins. This article summarizes the work that has been carried out in determining the character and properties of the resin constituents. Suggestions are also made regarding current thoughts of the role of these constituents on the structure and stability of petroleum.     

PHYSICAL AND CHEMICAL CHARACTERIZATIONS OF ASPHALTENES FROM DIFFERENT SOURCES

Asphaltenes and resins are two of the several, but important, heavy organics present in petroleum fluids. Asphaltenes are operationally defined as the non-colatile and polar fraction of petroleum that is insoluble in n-alkanes (i.e., n-pentane). Conversely resins are defined as the non-colatile and polar fraction of petroleum that is soluble in n-alkanes (i.e., n-pentane), and aromatic solvents (i.e., toluene), and insoluble in ethyl acetate. A commonly accepted view in the petroleum chemistry is that crude oil asphaltenes form micelles which are stabilized by adsorbed resins kept in solution by aromatics. Two key parameters that control the stability of asphaltene micelles in a crude oil are the ratio of aromatics to saturates and that of resins to asphaltenes. When these ratios decrease, asphaltene micelles will coalesce and form larger aggregates. The precipitation of asphaltene aggregates can cause problems such as reservoir plugging and wettability reversal.     

原油乳状液稳定性研究Ⅰ界面压与乳状液稳定性

影响油包水型原油乳状液稳定性的最重要的因素是包在水滴周围的具有一定强度的界面膜的存在.从热力学角度看,加入表而活性剂会降低界面张力,而界面张力越低,乳状液就越稳定这可部分解释表面活性剂能稳定乳状液的原因但彭响乳状液稳定性的更重要的是动力学问题界而膜的强度是影响乳状液稳定性动力学的最重要的因素之一,而界血压则是与界面膜强度密切相关的重要参数通过理论分析和对以胶质、沥青质组分为表而活性剂乳化形成的乳化液稳定性与界面压的研究,证明界面压(而不是界面张力)是度量乳状液稳定性的一个重要参数L当表而活性剂类型一定时.可以用界面压的大小来衡量乳状液稳定性的高低.     

甜菜碱溶液的界面性能及其在稠油降粘中的应用

为探索稠油乳化降黏过程中乳化剂的构效关系,考察了直链烷基甜菜碱(ASB)、二甲苯基取代甜菜碱(BSB)与稠油的油/水动态界面张力和界面扩张流变参数,测定了甜菜碱溶液与稠油形成的乳状液的稳定性、粒径和黏度。结果表明：甜菜碱分子的亲水基团平铺在界面上,形成具有一定弹性和强度的油/水界面膜,易与稠油形成稳定的O/W乳状液,显著降低了油相黏度。当油/水体积比为1∶1时,2种甜菜碱在质量分数为0.1%～1.0%的范围内,降黏率大于98%。ASB分子与稠油中活性物质混合吸附、协同作用,具有比BSB更高的界面活性和更强的稳定稠油乳状液能力,能在更宽的油/水体积比范围内有效降黏。