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     

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.     

MICROSCOPIC INVESTIGATION OF THE ONSET OF ASPHALTENE PRECIPITATION

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.     

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.     

Methodology for Predicting the Phase Envelope of a Heavy Crude Oil and Its Asphaltene Deposition Onset

Abstract

We have presented general ideas to develop a new theoretical methodology, based on molecular simulation and equations of state, for obtaining the phase envelope and to predict pressure, volume, temperature (PVT) conditions of asphaltene precipitation by only taking into account the composition of the heavy crude oil and an asphaltene average molecular structure. Those results show that asphaltene precipitation is a reversible thermodynamic process. The precipitated phase is a liquid phase which consists of mainly asphaltene and some heavy fractions from the crude. This methodology can be applied to find complete phase diagrams of different crude oils based on an asphaltene average molecular structure and the composition of crude oil.     

A comprehensive experimental evaluation of asphaltene dispersants for injection under reservoir conditions

As the efficiency of dispersants with different origins is questionable for each typical oil sample, the present study provides a reproducible and reliable method for screening asphaltene dispersants for a typical asphaltenic crude oil. Four different asphaltene dispersants (polyisobutylene succinimide, polyisobutylene succinic ester, nonylphenol-formaldehyde resin modified by polyamines, and rapeseed oil amide) were prepared and their performance on two oils from an Iranian field under laboratory and reservoir conditions was studied. A thorough analysis including ash content and SARA tests was performed on the solid asphaltene particles to characterize the nature of deposits. Then a highly efficient carrier fluid, which is crucial when injecting dispersant into the wells, was selected from a variety of chemicals by comparing their solubility. In the next step, using an optical microscope, a viscometer, and a Turbiscan, the screening of dispersants under laboratory conditions was done on a mixture of dead oil and dispersant to evaluate the onset of asphaltene precipitation and its stability when titrating by a precipitant. Finally, two different mixtures of the efficient dispersants, live oil, and carrier fluid were used with the solid detection system (SDS) and the filtration method to examine their effects on the onset pressure of asphaltene precipitation and the asphaltene content of the crude oil under reservoir conditions. The results show that the combination of experimental methods used in this work could be consistently applied to screening asphaltene dispersants. Among the four different dispersants applied here, the dispersant based on nonylphenol-formaldehyde resin modified by polyamines showed the best performance on the available live oils. This chemical modified the onset pressure of asphaltene precipitation of light oil from 4300 psi to about 3600 psi and decreased the precipitated asphaltene of heavy oil by about 30 %.     

Effect of pressure of the onset of asphaltene precipitation during gas flooding

In order to prevent and eliminate the asphaltene precipitation during gas flooding, the rules of the changes of the pressure under different conditions are systematically studied by the laser solid detection system, the light transmission method, and the P–T phase diagram when the asphaltene precipitation occurs. When the pressure is reducing to a certain value, the penetrating light intensity of the crude oil is markedly decreased, which shows that the pressure at this point is the pressure of the onset of asphaltene precipitation (AOPP). The AOPP value decreases with an increase in the temperature. During gas flooding, the AOPP value increases with an increase in the content of gas in the crude oil, and these two nearly do have a linear relationship. According to the P–T phase behaviors of the gas–crude oil system, with an increase in the content of gas in the crude oil, the asphaltene precipitation envelope curve (APE) is gradually moved up, which shows that the possibility of asphaltene precipitation is much higher. During oil production, for the oil reservoirs with rich asphaltene, the production pressure drop should be kept a small value to ensure that the flowing bottom-hole pressure is higher than AOPP and it is necessary to help complement producing energy timely by using water injection, gas injection, etc. Besides, according to the intersection of T–P curve and APE curve in the P–T phase diagram, the location where the asphaltene precipitation occurs in the wellbore can be roughly predicted. The experimental results can provide the theoretical foundation for taking measures to prevent and eliminate the asphaltene precipitation.     

Prediction of Asphaltene Precipitation during Pressure Depletion and CO2 Injection for Heavy Crude

Abstract

In this work, a thermodynamic approach is used for modeling the phase behavior of asphaltene precipitation. The precipitated asphaltene phase is represented by an improved solid model, and the oil and gas phases are modeled with an equation of state. The Peng-Robinson equation of state (PR-EOS) was used to perform flash calculations. Then, the onset point and the amount of precipitated asphaltene were predicted. A computer code based on the solid model was developed and used for predicting asphaltene precipitation data reported in the literature as well as the experimental data obtained from high-pressure, high-temperature asphaltene precipitation experiments performed on Sarvak reservoir crude, one of Iranian heavy oil reserves, under pressure depletion and CO₂ injection conditions. The model parameters, obtained from sensitivity analysis, were applied in the thermodynamic model. It has been found that the solid model results describe the experimental data reasonably well under pressure depletion conditions. Also, a significant improvement has been observed in predicting the asphaltene precipitation data under gas injection conditions. In particular, for the maximum value of asphaltene precipitation and for the trend of the curve after the peak point, good agreement was observed, which could not be found in the available literature.     

An Experimental Investigation of Asphaltene Precipitation During Natural Production of Heavy and Light Oil Reservoirs: The Role of Pressure and Temperature

Abstract

Many oil reservoirs encounter asphaltene precipitation as a major problem during natural production. In spite of numerous experimental studies, the effect of temperature on asphaltene precipitation during pressure depletion at reservoir conditions is still obscure in the literature. To study their asphaltene precipitation behavior at different temperatures, two Iranian light and heavy live oil samples were selected. First, different screening criteria were applied to evaluate asphaltene instability of the selected reservoirs using pressure, volume, and temperature data. Then, a high pressure, high temperature filtration (HPHT) setup was designed to investigate the asphaltene precipitation behavior of the crude samples throughout the pressure depletion process. The performed HPHT tests at different temperature levels provided valuable data and illuminated the role of temperature on precipitation. In the final stage, the obtained data were fed into a commercial simulator for modeling and predicting purposes of asphaltene precipitation at different conditions. The results of the instability analysis illustrated precipitation possibilities for both reservoirs which are in agreement with the oil field observations. It is observed from experimental results that by increasing the temperature, the amount of precipitated asphaltene in light oil will increase, although it decreases precipitation for the heavy crude. The role of temperature is shown to be more significant for the light crude and more illuminated at lower pressures for both crude oils. The results of thermodynamic modeling proved reliable applicability of the software for predicting asphaltene precipitation under pressure depletion conditions. This study attempts to reveal the complicated role of temperature changes on asphaltene precipitation behavior for different reservoir crudes during natural production.     

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.     

Investigation of Asphaltene Precipitation Process for Kuwaiti Reservoir

Abstract

As part of an Enhanced Oil Recovery (EOR) research program, Asphalting precipitation processes were investigated for a Kuwaiti dead oil sample using different hydrocarbons and carbon dioxide as precipitants at the ambient and high pressure of 3000 psig conditions. The hydrocarbons used as precipitants were ethane (C2), propane (C3), butane (C4), normal pentane (n-C5), normal hexane (n-C6), and normal heptane (n-C7). The equipment used for this investigation was a mercury-free, variable volume, fully visual JEFRI-DBR PVT system with laser light scattering. The minimum critical value of precipitants concentration for the oil sample has been identified at the ambient and high-pressure conditions for each precipitant. Our investigation has revealed that for this oil sample the most powerful asphaltene precipitant were CO₂ followed by C2, C3, C4, n-C5, n-C6, and n-C7. Moreover, the effect of pressure and temperature on the asphaltene precipitation has been investigated experimentally for CO₂, n-C5, n-C6, and n-C7. The precipitation and redissolution of asphaltene upon the addition and removal of CO₂ and light alkanes (C2–C4), at 3000 psig and ambient temperatures, have shown evidence of reversibility of asphaltene precipitation. A comprehensive fluid characterization analysis for the oil sample has been performed including, physical properties of crude oil, compositional, molecular weight (Mw), and SARA analyses. Advanced analytical techniques such as 1H and 13C NMR and IR spectrometers have been utilized to investigate the molecular structure of the asphaltene for this sample. It was concluded that the asphaltene molecules for this oil contain 120 total aromatic carbons with 42 aromatic rings, 114 naphthenic rings, and 5–7 sets of condensed aromatic rings.     

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     

A Thermodynamic Model for the Prediction of Asphaltene Precipitation

Abstract

Asphaltene precipitation in reservoirs, wells, and facilities can have a severe and detrimental impact on the oil production. Due to the extreme chemical complexity of the asphaltene and crude oil and the lack of comprehensive experimental data, the modeling of asphaltene precipitation in crude oil remains as a challenging task. In this article, a compositional thermodynamic model was developed to predict asphaltene precipitation conditions. The proposed model is based on a cubic equation of state with an additional term to describe the association of asphaltene molecules. Extensive testing against the literature data, including asphaltene precipitation from crude oil and solvent injection systems, concludes that the proposed model provides reasonable predictive results.     

Kinetics of CO2-induced asphaltene precipitation from various Saskatchewan crude oils during CO2 miscible flooding

A molar CO₂ programmed titration technique was used to evaluate the kinetics of CO₂-induced asphaltene precipitation from three Saskatchewan crude oils (namely Steelman, 12-25-6-14w2 and D8-12-6-14w2) under isothermal (in the range of 300–338 K) and isobaric (at 17.2 MPa) reservoir conditions in a solids detection system (SDS) consisting essentially of a mercury-free, variable volume, fully visual, JEFRI PVT cell. The results show that the rate of asphaltene precipitation depends on, both, the asphaltene and CO₂ contents of the oil. This work represents the first attempt at obtaining kinetic data for asphaltene precipitation from crude oil without any pretreatment of the oil as well as formulating a kinetic model that fits the data. Different values for the reaction order (m) of asphaltene, and the reaction order (n) for CO₂ were obtained for the same oil at different temperatures. This shows that the mechanism for CO₂-induced asphaltene precipitation was temperature dependent. Also, the values of n for all the oils at all the temperatures were much larger than the corresponding values for m. This shows that asphaltene precipitation is extremely more sensitive to CO₂ content than asphaltene content, even though the contribution from asphaltene content in the oil cannot be ignored. The large overall reaction order (m+n>4) also provides the experimental evidence to confirm that asphaltene precipitation is not an elementary process.     

The Importance of Asphaltene Content in Petroleum II—Multi-peak Viscosity Correlations

Abstract

It is common knowledge in petroleum science and technology that viscosities of dead crude oil are monotonic functions of oil's asphaltene content. However, analysis of crude oil databases reveals multiple peaking of oil viscosity (up to two orders of magnitude) at specific asphaltene contents, close to structural phase boundaries observed in asphaltene and oil solutions. Due to strong viscosity-density correlation, maxima of viscosity practically coincide with earlier reported maxima of specific gravity in dead crude oils.     

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.     

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.     

The Importance of Asphaltene Content in Petroleum—The Revision of Some Persistent Stereotypes

Abstract

It is common knowledge in petroleum science and technology that the bulk properties of a crude oil are monotonic functions of its asphaltene content. However, unbiased analysis of the world's crude oil databases reveals common peaking of oil density as well as of a frequency of oil appearance at specific asphaltene contents, close to structural phase boundaries observed in asphaltene and oil solutions. Another result of database analysis is a new analytical expression for the general trend of density-asphaltene relationship in the world's recovered (dead) crude oils.