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.     

Study of Asphaltene Precipitation Using Refractive Index Measurement

Abstract

The measurements of the refractive index of crude oils were utilized in this work to enhance the understanding of the behavior of asphaltenes in crude oil, specifically, their tendency to precipitate from crude oil. The onset of asphaltene precipitation was measured in eight crude oil samples, which were titrated with either heptane or pentane in order to induce precipitation of the asphaltenes. The refractive index of each sample was measured to find its relationship to asphaltene precipitation. The assumption that refractive index of a mixture is a linear combination of the refractive indexes of the individual components was verified. It was also found that mixtures of heptane or pentane and crude oil also followed this same behavior. However, as asphaltenes began to precipitate from the solution, the refractive index no longer followed this linear mixing rule. Careful analysis of the refractive index data for each of the crude oil samples revealed many interesting relationships between the refractive index data and the content of the different polar asphaltene fractions present. The refractive index of asphaltenes was predicted from the refractive index data of crude oils. The results suggest the possibility predicting the properties and characteristics of the asphaltenes contained in a crude oil simply by measuring the refractive index.     

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.     

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.     

Study of Asphaltene Precipitation Using Refractive Index Measurement

The measurements of the refractive index of crude oils were utilized in this work to enhance the understanding of the behavior of asphaltenes in crude oil, specifically, their tendency to precipitate from crude oil. The onset of asphaltene precipitation was measured in eight crude oil samples, which were titrated with either heptane or pentane in order to induce precipitation of the asphaltenes. The refractive index of each sample was measured to find its relationship to asphaltene precipitation. The assumption that refractive index of a mixture is a linear combination of the refractive indexes of the individual components was verified. It was also found that mixtures of heptane or pentane and crude oil also followed this same behavior. However, as asphaltenes began to precipitate from the solution, the refractive index no longer followed this linear mixing rule. Careful analysis of the refractive index data for each of the crude oil samples revealed many interesting relationships between the refractive index data and the content of the different polar asphaltene fractions present. The refractive index of asphaltenes was predicted from the refractive index data of crude oils. The results suggest the possibility predicting the properties and characteristics of the asphaltenes contained in a crude oil simply by measuring the refractive index.     

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.     

DIBSOLUTION OF SOLID BOBCAN ASPHALTENES IN MIXED SOLVENTS.

ABSTRACT

Solid petroleum asphaltenes have been fractionated according to solubility in toluene/n-heptane mixtures of increasing toluene content. A large hysteresis was observed between this dissolution and the precipitation from the crude oil. In order to shed light on the solution mechanism, the fractions obtained have been analyzed using size exclusion chromatography (SEC-HPLC-UV-vis), VPO, elemental analysis, UV-vis adsorption spectroscopy and phenol interaction values and methylene content by FTir. Less polar non-associating low molecular weight species are dissolved and a specific extraction of porphyrins is observed. An increased association in the insolubles is indicated. More basic interaction sites are available on the asphaltenes in both fractions relative to the native asphaltene. From the SEC chromatograms it was seen that the soluble fractions did not associate as the insoluble fractions even when making up more than 60 % of the total asphaltenes.     

Deposition and flocculation of asphaltenes from crude oils

A crude oil has four main constituents: saturates, aromatics, resins, and asphaltenes. The asphaltenes in crude oil are the most complex and heavy organic compounds. The classic definition of asphaltenes is based on the solution properties of petroleum residuum in various solvents. Asphaltenes are a solubility range that is soluble in light aromatics such as benzene and toluene, but are insoluble in lighter paraffins. The particular paraffins, such as n-pentane and n-heptane, are used to precipitate asphaltenes from crude oil. Deposition of asphaltenes in petroleum crude and heavy oil can cause a number of severe problems. The precipitation of asphaltene aggregates can cause such severe problems as reservoir plugging and wettability reversal. Asphaltenes can precipitate on metal surface. Cleaning the precipitation site as well as possible appears to slow reprecipitation. To prevent deposition inside the reservoir, it is necessary to estimate the amount of deposition due to various factors. The processes can be changed to minimize the asphaltene flocculation, and chemical applications can be used effectively to control depositions when process changes are not cost effective. Asphaltene flocculation can be controlled through better knowledge of the mechanisms that cause its flocculation in the first place. The processes can be controlled to minimize the asphaltene flocculation, and chemical applications can be used effectively to control depositions when process changes are not cost effective.     

An experimental study on electrical effect on asphaltene deposition

Asphaltene generally existed in colloidal form in cruds and will precipitate in non-equilibrium conditions. Asphaltene instability may take place in the reservoir leading to permeability damage and contributing to flow restriction issues. It may also occur in production strings and surface facilities causing pipe blockage. Any change in oil composition or pressure and temperature at any stage of production will destabilize crude oil producing asphaltene precipitation. In this paper, the stability of target crude oil under the influence of a direct current and contacting with polar fluid, water, is investigated. The amount of the asphaltene deposit and its electrical charge at various operating conditions are investigated. The fact that deposits form on the anode surface proves that asphaltene particles possess a positive charge. The amounts of asphaltenes precipitation were increased considerably by increasing water as polar component.     

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     

不同极性的乙烯-醋酸乙烯酯共聚物对原油中沥青质分散稳定性的影响

以储罐储存的阿曼原油及不同醋酸乙烯酯基团(VA)含量的乙烯-醋酸乙烯酯共聚物(EVA)为研究对象,通过实验研究了添加EVA前后原油中沥青质的动态稳定性、离心稳定性及粒度分布的变化,进而探讨了在相同相对分子质量的情况下,VA基团含量对EVA分散稳定沥青质作用的影响。结果表明,VA基团质量分数为30%的EVA分散稳定沥青质的作用最强;EVA通过吸附于沥青质表面,抑制沥青质絮凝沉淀,从而起到分散稳定沥青质的作用;非极性基团的空间阻碍作用和EVA与沥青质间的吸附作用共同影响了EVA分散稳定沥青质的效果;增加VA含量会导致EVA中非极性链的数量和长度减小,减弱EVA非极性链的空间阻碍作用,从而减弱EVA分散稳定沥青质的效果。分子动力学模拟表明,增加VA含量会增强EVA与沥青质的吸附作用,从而提高EVA分散稳定沥青质的效果。     

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.     

MOLECULAR MECHANICS OF AGGREGATES OF ASPHALTENES AND RESINS OF THE ATHABASCA OIL

An analysis of the effects of an almost continuous chemical distribution of asphaltenes and resins on the molecular recognition processes occurring in crude oil indicates that their aggregates will have a broad distribution both in the chemical composition and in the strength of the intermolecular interactions responsible for the aggregation. Then, crude oil cannot be described just as a sol formed by solid asphaltene particles dispersed by resins or as a simple micellar system of asphaltene and resin molecules. The molecular aggregates may vary from solid particles formed by asphaltenes and resins to loosely bound micelles with quite short lifetimes. These different aggregates may coexist within the crude oil and many will exchange components with others. The entropic contributions to the changes in free energy upon aggregation were also discussed. Molecular mechanics calculations showed that a model asphaltene aggregate from Athabasca exhibits stronger interactions with its resins than with solvents such as toluene and n-octane. The resins showed a considerable selectivity for the different adsorption sites of the asphaltene aggregate. This selectivity was stronger than that found for the solvent molecules, indicating that it is enthalpically more favorable for them to form aggregates with the asphaltenes. The selectivity may also help to explain the specificity of some resins that are able to disperse only the asphaltenes of certain types of crude oils while failing to do the same for others.     

Development of an Artificial Neural Network Algorithm for the Prediction of Asphaltene Precipitation

Abstract

The precipitation and deposition of crude oil polar fractions such as asphaltenes in petroleum reservoirs considerably reduce rock permeability and oil recovery. Therefore, it is of great importance to determine how and how much the asphaltenes precipitate as a function of pressure, temperature, and liquid phase composition. The authors designed and applied an Artificial Neural Network (ANN) model to predict the amount of asphaltene precipitation at a given operating condition. Among this training, the back-propagation learning algorithm with different training methods was used. The most suitable algorithm with an appropriate number of neurons in the hidden layer, which provides the minimum error, was found to be the Levenberg-Marquardt (LM) algorithm. An extensive experimental data for the amount of asphaltene precipitation at various temperatures (293–343 K) was used to create the input and target data for generating the ANN model. The predicted results of asphaltene precipitation from the ANN model was also compared with the results of proposed scaling equations in the literature. The results revealed that scaling equations cannot predict the amount of asphaltene precipitation adequately. With an acceptable quantitative and qualitative agreement between experimental data and predicted amount of asphaltene precipitation for all ranges of dilution ratio, solvent molecular weight and temperature was obtained through using ANN model.     

A new experimental investigation on upgrading of waxy crude oils by methacrylate polymers

Several methods have been used to reduce problems caused by wax precipitation during the production and/or transportation of waxy crude oil. Polymers are used to improve pour point and rheological behavior of waxy crude oils. In this work, the influence of the polymer inhibitors such as methacrylate polymers, as wax inhibitor, with different range of molecular weight and alkyl side chain carbons on the rheological behavior and pour point of two Iranian waxy crude oils were evaluated. Two Iranian waxy crude oils were selected on the basis of wax and asphaltene contents. The rheological behavior of these crude oils in absence and in presence of methacrylate polymer was studied. The rheological data cover the temperature range of–1 to 12°C. The results indicated that the performance of methacrylate polymer was dependent on the molecular weight, alkyl side chain carbons and the asphaltene content of crude oil. Methacrylate polymers with longer alkyl side chains than 18 carbons would perform best as wax inhibitors in two cases. Also, for crude oil with low asphaltene, higher molecular weight methacrylate polymer is the best flow improver and lower molecular weight methacrylate polymer showed good efficiency for crude oil with high asphaltene content.     

一种新型原油降黏剂的合成及降黏机理研究

为了降低原油黏度,提高其采收率,结合原油组分的特征,以苯乙烯、马来酸酐和壬基酚聚氧乙烯醚3种单体分两步合成了新型油溶性原油降黏剂SMN。考察SMN对胜利高黏度原油的降黏效果,发现该原油降黏率最高可以达到68.5%。通过机理探究推测SMN中的苯环、羧基和酯基等极性较大的基团可以通过氢键作用和π-π堆积进入到沥青质片层中,而分子中具有较大位阻的乙氧基能够阻止沥青质聚集,从而分散原油中的重组分,降低原油的黏度。     

MICROSCOPIC INVESTIGATION OF THE ONSET OF ASPHALTENE PRECIPITATION

ABSTRACT

A microscopic study of the onset of asphaltene precipitation is reported. The onset conditions can be quantified by measurement of mixture refractive index, together with microscopic observations of particulate formation in mixtures of oil and precipitant, with or without added solvents. For isooctane mixtures with a variety of hydrocarbon solvents and a crude oil from Alaska, the onset of precipitation occurs over a narrow range of solution refractive index. Addition of polar solvents or different precipitating agents can shift the refractive index at which precipitation begins. Refractive index decreases when a crude oil is diluted by precipitant, as in this study, or when changes in temperature and pressure alter the relative molar volumes of species in the oil. If it falls below some critical value, resin/asphaltene aggregates that had been in stable dispersion become unstable and precipitate. These observations provide a method of screening solvents to differentiate between those that prevent precipitation mainly by maintaining a higher mixture refractive index and others that may participate in or disrupt asphaltene/resin interactions.     

Intelligent Modeling of Asphaltene Precipitation in Live and Tank Crude Oil Systems

Abstract

The study of asphaltene precipitation properties has been motivated by their propensity to aggregate, flocculate, precipitate, and adsorb onto interfaces. The tendency of asphaltenes to precipitation has posed great challenges for the petroleum industry. The most important parameters in asphaltene precipitation modeling and prediction are the asphaltene and oil solvent solubility parameters, which are very sensitive to reservoir and operational conditions. The driving force of asphaltene flocculation is the difference between asphaltene and the oil solvent solubility parameter. Since the nature of asphaltene solubility is yet unknown and several unmodeled dynamics are hidden in the original systems, the existing prediction models may fail in prediction the asphaltene precipitation in crude oil systems. One of ways in modeling such systems is using intelligent techniques that need some information about the systems; so, based on some intelligent learning methods it can provide a suitable model. The authors introduce a new implementation of the artificial intelligent computing technology in petroleum engineering. They have proposed a new approach to prediction of the asphaltene precipitation in crude oil systems using fuzzy logic, neural networks, and genetic algorithms. Results of this research indicate that the proposed prediction model with recognizing the possible patterns between input and output variables can successfully predict and model asphaltene precipitation in tank and live crude oils with a good accuracy.     

The Role of Asphaltene Solubility and Chemical Composition on Asphaltene Aggregation

Abstract

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.     

Test Methods for Determining Asphaltene Stability in Crude Oils

Abstract

The high cost of remediating asphaltene deposition in crude oil production and processing has necessitated the development of test methods for determining the stability of asphaltenes in crude oils. In the current work, the stability of asphaltenes in crude oils of varying API gravity is predicted using the Oliensis Spot Test, the Colloidal Instability Index, the Asphaltene–Resin ratio, and a solvent titration method with NIR solids detection. The test methods are described in detail and experimental data from them presented. The experimental stability data were validated via correlation with field deposition data. The effectiveness of the various tests as predictors of the stability of asphaltenes in oils is discussed. The Colloidal Instability Index and the solvent titration method were found to predict a crude oil's propensity towards asphaltene precipitation better than both the Asphaltene–Resin ratio and the Oliensis Spot Test. For oils with low asphaltene content where most stability tests fail, live oil depressurization is proposed as the test for predicting the stability of asphaltenes.