The Solubility and Three-Dimensional Structure of Asphaltenes

The tendency of the asphaltenes to form aggregates in hydrocarbon solution is one of their most characteristic features and has tended to complicate the determination of the structure of petroleum In addition, if the composition and properties of the precipitated asphaltenes reflect those of the micelles in solution, the latter should be considered as mixed micelles. This is a reasonable assumption in view of the large quantities of soluble resins found in the precipitated solid

Empirical observations indicate that the resins play an important role in stabilizing asphaltenes in crude oil and under unfavorable solvent conditions the asphaltene species are prone to further aggregation into clusters that are unstable and precipitate from the crude oil. It is also suggested that the resins and the asphaltenes from a particular crude oil have points of structural similarity relative to the asphaltenes and resins from another crude oil. On a more localized scale, i.e. in one particular crude oil there are also structural differences within the constituents of asphaltenes and structural differences within the constituents of the resins are also anticipated

Therefore, the structure of the micelles within any one crude oil must be expected to be varied and non-homogenous. From the evidence cited herein, it follows that the potential for graphite-type stacking by the asphaltene molecules in the center of a micelle might not be as great as the potential for the micelles forming by asphaltene-resin interactions rather than by asphaltene-asphaltene interactions     

Crude oil aggregation by microscopy and dynamic light scattering

This research is focused on establishing a methodology to evaluate the aggregation state of Mexican crude oil solutions from two different sources and SARA compositions, by using Dynamic Light Scattering (DLS). Different crude oil concentrations were established and monitored through time in order to determine their effects on the aggregation state. DLS results indicate that the aggregation state of the studied solutions is influenced by crude oil composition, specifically by the amount of resins. Particle size and elemental analysis of the aggregates were performed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX), respectively. Results from these techniques reveal particulated low-porosity smooth surfaces due to the presence of resin, as well as the determination of the characteristic elements found in asphaltenes. High-Resolution Transmission Electron Microscopy (HTEM) indicated the presence of asphaltene aggregates constituted by nanometric particles and asphaltene stacking as well as ultrafine nanocrystalline-oriented structures.     

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。     

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.     

Assembly of asphaltene molecular aggregates as studied by near-UV/visible spectroscopy: II. Concentration dependencies of absorptivities

The properties of molecular aggregation in toluene solutions of a crude oil and solid asphaltenes are determined almost solely by the concentration of asphaltenes, as shown by absorptivity measurements at 315–750 nm. From non-monotonic concentration dependencies of absorptivities, it is concluded that asphaltene monomers are abundant in solutions with asphaltene concentrations below 1–5 mg/l, while molecular aggregates are effectively formed above 20–25 mg/l. The most stable oligomers are a dimer and a dimer pair (Yen's “nanocrystallite” [NC]). Nanocrystallites act as building blocks for more complex aggregates at asphaltene concentrations exceeding 90–100 mg/l. These optical absorption results are supported by studies of Rayleigh scattering in asphaltene solutions.     

Metal porphyrin occlusion: Adsorption during asphaltene aggregation

Metal compounds such as vanadyl and nickel porphyrins present in crude oils are associated to the most polar fraction defined as asphaltenes. The amount and kind of these compounds in the crude oil depend of the variations in origin, maturity, pressure, and temperature. During the asphaltene colloid formation the metal porphyrins could be trapped, occluded, or adsorbed, protecting these compounds from oxidation or chemical degradation. In this work the authors induce the aggregation of asphaltenes by changing the solubility parameter of the media in presence of metal porphyrins. UV-vis absorbance is used to monitored asphaltene aggregation at 350 nm to follow the variations in asphaltene aggregation and 405 nm to follow the porphyrin Soret band. The results showed that more than 50% of the porphyrins were trapped inside the asphaltene aggregate and posterior re-dissolution of the aggregates in toluene showed very low release of the porphyrins, demonstrating the strong interaction between the porphyrin and asphaltenes during the aggregation.     

PHYSICAL AND CHEMICAL CHARACTERIZATIONS OF ASPHALTENES FROM DIFFERENT SOURCES

ABSTRACT

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.     

PEPTIZATION AND COAGULATION OF ASPHALTENES IN APOLAR MEDIA USING OIL-SOLUBLE POLYMERS

The asphaltene fraction of crude oil contains a variety of acidic and basic functional groups. During oil production and transportation, changes in temperature, pressure or oil composition can cause asphaltenes to precipitate out crude oil through the flocculation among these polar functional groups. In this study, two types of oil-soluble polymers, dodecylphenolic resin and poly (octadecene maleic anhydride), were synthesized and used to prevent asphaltenes from flocculating in heptane media through the acid-base interactions with asphaltenes. The experimental results indicate that these polymers can associate with asphaltenes to either inhibit or delay the growth of asphaltene aggregates in alkane media. However, multiple polar groups on a polymer molecule make it possible to associate with more than one asphaltene molecule, resulting in the hetero-coagulation between asphaltenes and polymers. It was found that the size of the asphaltene-polymer aggregates was strongly affected by the polymer-to-asphaltene weight (or number) ratio. At low polymer-to-asphaltene weight ratios, asphaltenes keep flocculating with themselves and with polymers until the floes precipitate out of solution. On the other hand, at high polymer-to-asphaltene weight ratios, asphaltene-polymer aggregates peptized by the extra polymer molecules can remain fairly stable in the solution.     

PEPTIZATION AND COAGULATION OF ASPHALTENES IN APOLAR MEDIA USING OIL-SOLUBLE POLYMERS

ABSTRACT

The asphaltene fraction of crude oil contains a variety of acidic and basic functional groups. During oil production and transportation, changes in temperature, pressure or oil composition can cause asphaltenes to precipitate out crude oil through the flocculation among these polar functional groups. In this study, two types of oil-soluble polymers, dodecylphenolic resin and poly (octadecene maleic anhydride), were synthesized and used to prevent asphaltenes from flocculating in heptane media through the acid-base interactions with asphaltenes. The experimental results indicate that these polymers can associate with asphaltenes to either inhibit or delay the growth of asphaltene aggregates in alkane media. However, multiple polar groups on a polymer molecule make it possible to associate with more than one asphaltene molecule, resulting in the hetero-coagulation between asphaltenes and polymers. It was found that the size of the asphaltene-polymer aggregates was strongly affected by the polymer-to-asphaltene weight (or number) ratio. At low polymer-to-asphaltene weight ratios, asphaltenes keep flocculating with themselves and with polymers until the floes precipitate out of solution. On the other hand, at high polymer-to-asphaltene weight ratios, asphaltene-polymer aggregates peptized by the extra polymer molecules can remain fairly stable in the solution.     

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.     

塔河超稠油胶质、沥青质形貌分析

用环境扫描电子显微镜观察稠油非烃组分胶质和沥青质的形貌,分析结果表明,胶质分子之间、沥青质分子之间以及二者之间可以发生相互作用,形成结构较大的颗粒,胶质颗粒之间连接紧密,沥青质颗粒之间较分散。胶质和沥青质的含量和平面堆砌结构是影响稠油粘度的因素。     

沥青质在高定向热解石墨表面络合机制的分子动力学模拟

沥青质在固体表面的络合机制是解决剩余油开采难题的重要理论基础。为了给聚集抑制剂和表面活性剂的开发提供理论依据,采用分子动力学模拟,系统研究了沥青质在高定向热解石墨表面附着、聚集的特征。通过计算表面吸附过程中沥青质的自由能变化,基于Yen-Mullins模型的定量判据,结合沥青质平均相互作用分子数和分子密度分布,定量分析了沥青质在固-液界面体系与溶液体系中聚集作用的差异。分子动力学模拟分析表明,固体表面会降低沥青质的聚集程度,加快聚集过程中的阶段分化,具体包括4个阶段的界面过程：①沥青质覆盖固体表面并逐渐铺满一层;②固体表面上形成纳米聚集体;③固体表面上纳米聚集体与溶液中的纳米聚集体通过边缘堆叠、T形堆叠形成簇状物;④固体表面的聚集体与溶液中的聚集体通过脂肪侧链接触形成絮凝物。     

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.     

Influence of the properties of resins on the interactions between asphaltenes and resins

The properties of two resins (Tahe resin and Liaohe resin) and their influences on the dispersion of two asphaltenes (Tahe asphaltene and Liaohe asphaltene) are investigated by laboratory experiments. The results indicate that the adsorption isotherms of two resins are accorded with the Freundlich absorption model. The shape of the curves obtained could be attributed to both multilayer adsorption of resins on asphaltenes surfaces and the penetration of resins into the microporous structure of the asphaltenes. Based on the combined results from the shape of the curves and chemical properties of resins, the relative adsorption quantity of Tahe resin is higher than that of Liaohe resin due to the stronger polarity of Tahe resin, and the effect of Tahe resin on the dispersion of asphaltene is stronger than that of Liaohe rein. The different properties of resin can directly lead to the difference of dispersion performance on asphaltene in crude oil, which is closely related to the chemical structure of resin. The more the number of aromatic structure of the resin, the stronger the effect of resin on the dispersion of asphaltene there is.     

ASPHALTENE PRECIPITATION AND SOLVENT PROPERTIES OF CRUDE OILS

Improved prediction of the onset of asphaltene precipitation may be achieved using refractive index (RI) to characterize crude oils and their mixtures with precipitants and solvents. Experimental measurements of RI for mixtures of several crude oils with the precipitant n-heptane, are reported at ambient conditions. Theoretical developments are described that will permit extension of these observations to reservoir conditions

Measurements of RJ at the onset of precipitation have shown that the onset occurs at a characteristic RI for each oil/ precipitant combination, supporting the premise that precipitation is dominated by London dispersion interactions and thus, that RI can be used to predict the onset of precipitation. Reports in the literature showing that the onset of precipitation occurs at constant solvent-to-precipitant ratios provide additional confirmation

The theory is developed on the assumption that London dispersion forces dominate aggregation and precipitation of asphaltenes. The interaction energy of asphaltene molecules or aggregates in a medium of oil can be expressed as a function of the difference between the RI of asphaltene and oil. The RI of live crude oil during pressure depletion can be calculated from the RI of the stock tank oil, the molar refraction of the separator gas, the formation volume factor B_o and the solution gas/ oil ratio R_s     

INTERMOLECULAR FORCES IN AGGREGATES OF ASPHALTENES AND RESINS

In order to determine the forces acting in the asphaltene and resin molecular aggregates, an analysis of the origin of the intermolecular interactions in organic molecules was made. The results showed that the forces present in the aggregates of asphaltenes and resins were only those originated in the van der Waals, Coulombic (electrostatic), charge transfer and induction plus the exchange-repulsion interaction. No other forces were found to be significant in these aggregates that are formed by molecules containing well-known atomic groups. Molecular orbital calculations in resins and model asphaltene suggested that charge transfer is small or negligible in their aggregates. Although the H bonds present could be quite strong, other intermolecular interactions should not be disregarded in the analysis of the energy of their aggregates.     

REVERSIBILITY AND INHIBITION OF ASPHALTENE PRECIPITATION IN BRAZILIAN CRUDE OILS

A fundamental understanding of the aggregation and precipitation of asphaltenes in petroleum crudes is important for the development of preventive and curative measures for the potential problem of asphaltene deposition occurring during production, transport and refining operations. The question of reversibility of asphaltene precipitation, yet a controversial issue, is crucial for a clear and unequivocal understanding of the precipitation phenomenon, development of mathematical models that describe the behavior of asphaltenes in petroleum fluids, and the design of inhibitors. In this work, the behavior of precipitated asphaltenes in Brazilian crude tank oil samples following flocculant removal and gradual addition of fresh oil was investigated. The results obtained revealed a re-dissolution of precipitated asphaltene particles following flocculant removal and oil addition. On the inhibition of asphaltene precipitation, the capacity of a number of surfactants and block copolymers to inhibit asphaltene precipitation and deposition was also examined. Ethoxylated Nonylphenols and Hexadecyl Trimethyl Ammonium Bromide displayed highest capacity in the inhibition of asphaltene deposition.     

The Role of Asphaltene Solubility and Chemical Composition on Asphaltene Aggregation

Asphaltenes from four different crude oils (Arab Heavy, B6, Canadon Seco, and Hondo) were fractionated in mixtures of heptane and toluene and analyzed by small angle neutron scattering (SANS). Fractionation appeared to concentrate the most polar species into the least soluble sub-fraction as indicated by elemental analysis. SANS results indicated a wide spectrum of asphaltene aggregate sizes and molecular weights; however, the less soluble (more polar) fraction contributed the majority of the species responsible for asphaltene aggregation in solution. This more polar, less soluble fraction is likely the major cause for many petroleum production problems such as deposition and water-in-oil emulsion stabilization. A comparison of molecular weight and aggregate size indicated that asphaltenes formed fractal aggregates in solution with dimensions between 1.7 and 2.1. This was consistent with the “archipelago” model of asphaltene structure. Resins were shown to effectively solvate asphaltene aggregates as observed by an increase in asphaltene solubility, reduction in aggregate size and molecular weight, and an increase in the fractal dimension to ~ 3.     

ASPHALTENE PRECIPITATION AND SOLVENT PROPERTIES OF CRUDE OILS

ABSTRACT

Improved prediction of the onset of asphaltene precipitation may be achieved using refractive index (RI) to characterize crude oils and their mixtures with precipitants and solvents. Experimental measurements of RI for mixtures of several crude oils with the precipitant n-heptane, are reported at ambient conditions. Theoretical developments are described that will permit extension of these observations to reservoir conditions

Measurements of RJ at the onset of precipitation have shown that the onset occurs at a characteristic RI for each oil/ precipitant combination, supporting the premise that precipitation is dominated by London dispersion interactions and thus, that RI can be used to predict the onset of precipitation. Reports in the literature showing that the onset of precipitation occurs at constant solvent-to-precipitant ratios provide additional confirmation

The theory is developed on the assumption that London dispersion forces dominate aggregation and precipitation of asphaltenes. The interaction energy of asphaltene molecules or aggregates in a medium of oil can be expressed as a function of the difference between the RI of asphaltene and oil. The RI of live crude oil during pressure depletion can be calculated from the RI of the stock tank oil, the molar refraction of the separator gas, the formation volume factor B_o and the solution gas/ oil ratio R_s     

INTERMOLECULAR FORCES IN AGGREGATES OF ASPHALTENES AND RESINS

ABSTRACT

In order to determine the forces acting in the asphaltene and resin molecular aggregates, an analysis of the origin of the intermolecular interactions in organic molecules was made. The results showed that the forces present in the aggregates of asphaltenes and resins were only those originated in the van der Waals, Coulombic (electrostatic), charge transfer and induction plus the exchange–repulsion interaction. No other forces were found to be significant in these aggregates that are formed by molecules containing well-known atomic groups. Molecular orbital calculations in resins and model asphaltene suggested that charge transfer is small or negligible in their aggregates. Although the H bonds present could be quite strong, other intermolecular interactions should not be disregarded in the analysis of the energy of their aggregates.