Experimental and Modelling Investigations of Asphaltene Precipitation During Pressure Depletion and Gas Injection Operations

Asphaltene precipitation problems manifest themselves in different stages of oil reservoirs production. Experimental and modeling investigations are, therefore, employed as promising tools to assist in predictions of asphaltene precipitation problems and selection of proper production facilities. This study concerns experimental and modeling investigations of asphaltene precipitation during natural production and gas injection operations for a heavy Iranian crude oil at reservoir conditions. First, with design and performance of high pressure–high temperature experiments, asphaltene precipitation behavior is comprehensively investigated; the effects of pressure and temperature are fully studied during pressure depletion tests and the role of injection gas composition on precipitation is described in gas injection experiments. In the next stage, the obtained experimental results are fed into a commercial simulator to develop the asphaltene precipitation model. The results for the pressure depletion experiments indicate that the maximum amount of asphaltene precipitation takes place at fluid bubble point pressure. Increase in the temperature, as seen, causes to reduce the amount of precipitation for the entire range of pressures. For gas injection experiments, the onset of precipitation for CO₂, associated, and N₂ gases takes place at around 0.20, 0.28, and 0.50 gas to mixture mole ratios, respectively. Carbon dioxide shows the highest asphaltene precipitation values and nitrogen has the lowest amounts for the whole range of gas mole fractions. Finally, the results for modeling indicate successful asphaltene precipitation predictions for both pressure depletion and gas injection processes.     

The Impact of CO2 Injection and Pressure Changes on Asphaltene Molecular Weight Distribution in a Heavy Crude Oil: An Experimental Study

Abstract

This work concerns observing the pressure as well as CO₂ mole percentage effects on asphaltene molecular weight distributions at reservoir conditions. A high-pressure, high-temperature asphaltene measurement setup was applied, and the amount of precipitated asphaltene at different pressures as well as CO₂ mole percentage in an Iranian heavy crude oil was measured. Moreover, the asphaltene molecular weight distributions during titration of crude oil with different n-alkanes were investigated. The gel permeation chromatography (GPC) apparatus was used for characterization of asphaltene molecular weight under different conditions. It has been observed that some thermodynamic changes such as pressure depletion above the bubble point increase the average molecular weight of asphaltene and cause the asphaltene molecular weight distributions changes from a bimodal curve with two maxima to a single maxima curve. One the other hand, below the bubble point, pressure reduction causes a decrease in the average molecular weight of asphaltene and also causes the shape of asphaltene molecular weight distributions to restore, which might be due to dissolution of asphaltene aggregates. An interesting result is that asphaltene molecular weight distribution at the final step of pressure reduction tests, ambient condition, shows approximately the same trend as the distribution of asphaltene molecular weight obtained at reservoir condition. This behavior explains the reversibility of the asphaltene precipitation process under pressure depletion conditions. In the case of CO₂ injection, the graphs of asphaltene molecular weight distributions always show a single modal trend and shift toward larger molecular weight values when CO₂ mole percentage increases. The results of this work can be imported to thermodynamic models that use polydisperse data of heavy organic fractions to enhance their performance at reservoir conditions. The distributions obtained by this method are good indicators of asphaltene structures at reservoir conditions.     

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 Investigation of Asphaltene Precipitation During Natural Production and the CO2 Injection Process

Some of Iranian oil reservoirs suffer from operational problems due to asphaltene precipitation during natural depletion, so widely investigation on asphaltene precipitation is necessary for these reservoirs. In this study, a reservoir that is candidate for CO₂ gas injection process is selected to investigate asphaltene precipitation with and without CO₂ injection. In this case, asphaltene precipitation is monitored at various pressures and reservoir temperature. Then, a series of experiments are carried out to evaluate the amount of precipitated asphaltene by injection different molar concentrations (25%, 50%, and 75%) of CO₂. The results show that during primary depletion the amount of precipitated asphaltene increases with pressure reduction until bubble point pressure. Below the bubble point the process is reversed (i.e., the amount of precipitated asphaltene at bubble point pressure is maximum). The behavior of asphaltene precipitation versus pressure for different concentrations of CO₂ is similar to primary depletion. Asphaltene precipitation increases with CO₂ concentration at each pressure step. In the modeling part, solid model and Peng-Robinson equation of state are employed which show a good match with experimental results.     

Modeling Asphaltene Precipitation Under Gas Injection and Pressure Depletion Conditions

Asphaltene precipitation is a major problem during primary oil production and enhanced oil recovery in the petroleum industry. In this work, a series of experiments was carried to determine the asphaltene precipitation of bottom hole live oil during gas injection and pressure depletion condition with Iranian bottom hole live oil sample, which is close to reservoir conditions using high pressure-high temperature equilibrium cell. In the majority of previous works, the mixture of recombined oil (mixture dead oil and associated gas) was used which is far from reservoir conditions. The used pressure ranges in this work covers wide ranges from 3 to 35 MPa for natural depletion processes and 24–45 MPa for gas injection processes. Also, a new approach based on the artificial neural network (ANN) method has been developed to account the asphaltene precipitation under pressure depletion/gas injection conditions and the proposed model was verified using experimental data reported in the literature and in this work. A three-layer feed-forward ANN by using the Levenberg-Marquardt back-propagation optimization algorithm for network training has been used in proposed artificial neural network model. The maximum mean square error of 0.001191 has been found. In order to compare the performance of the proposed model based on artificial neural network method, the asphaltene precipitation experimental data under pressure depletion/gas injection conditions were correlated using Solid and Flory-Huggins models. The results show that the proposed model based on artificial neural network method predicts more accurately the asphaltene precipitation experimental data in comparison to other models with deviation of less than 5%. Also, the number of parameters required for the ANN model is less than the studied thermodynamic models. It should be noted that the Flory and solid models can correlate accurately the asphaltene precipitation during methane injection in comparison with CO₂ injection.     

Prediction of asphaltene precipitation in crude oil

Asphaltene are problematic substances for heavy-oil upgrading processes. Deposition of complex and heavy organic compounds, which exist in petroleum crude oil, can cause a lot of problems. In this work an Artificial Neural Networks (ANN) approach for estimation of asphaltene precipitation has been proposed. Among this training the back-propagation learning algorithm with different training methods were used. The most suitable algorithm with appropriate number of neurons in the hidden layer which provides the minimum error is found to be the Levenberg–Marquardt (LM) algorithm. ANN's results showed the best estimation performance for the prediction of the asphaltene precipitation. The required data were collected and after pre-treating was used for training of ANN. The performance of the best obtained network was checked by its generalization ability in predicting 1/3 of the unseen data. Excellent predictions with maximum Mean Square Error (MSE) of 0.2787 were observed. The results show ANN capability to predict the measured data. ANN model performance is also compared with the Flory–Huggins and the modified Flory–Huggins thermo dynamical models. The comparison confirms the superiority of the ANN model.     

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.     

Asphaltene Precipitation During Different Production Operations

Asphaltene precipitation due to enhanced oil recovery (EOR) methods or natural depletion is a serious technical problem at petroleum industry. The authors present the result of asphaltene precipitation during associated gas injection, CO₂ injection, and natural depletion in reservoir condition. In addition, the effect of variations in operation pressure, injection gas concentration, and production rate on asphaltene precipitation and difference between slope of precipitation graph due to various method of EOR or natural depletion were investigated. The results revealed that temperature has an efficient role on result of asphaltene deposition through associated gas and CO₂ injection. By decreasing temperature, the amount of asphaltene precipitation due to associated gas injection was increased. In fact, recovery of gas injection was decreased at lower temperatures, hence; solubility has an important rule on asphaltene precipitation.     

Prediction of asphaltene precipitation by the extended Flory–Huggins model using the modified Esmaeilzadeh–Roshanfekr equation of state

Asphaltene precipitation is caused by a number of factors, such as the variation of pressure and temperature, the change in composition and the mixing of oil with diluting solvents. The deposition of asphaltene precipitation is one of the main problems with the oil industries, appearing in the well bore, the well tubing and the refining processes. This causes an increase in the operating costs and imposes the costs of cleaning and washing well tubing as well. Therefore, it would be economically beneficial to know under what conditions and to what amount the asphaltene precipitates.In this paper, a model is presented based on the Flory–Huggins theory of polymeric solutions. Because the interaction parameter term plays a key role in the asphaltene precipitation, a correlation is proposed to account for the effect of the solvent ratio in addition to molecular weight. Several adjustable parameters in terms of the interaction parameter are determined in this work using a series of experimental precipitation data from a crude oil sample of a field located in the southwest of Iran (oil sample 1), and applying a robust optimization method (the differential evolution). Regarding the influence of the solubility parameter on the accuracy of the final results, a comparison is made between the m-ER, PR and the SRK EOSs. Finally, the obtained results from the comparison between the asphaltene precipitation amounts of various solvents and the existing experimental values for another group of data from oil sample 1, and two other oil samples verify the accuracy of the presented model.     

Prediction of asphaltene precipitation from n-alkane diluted crude oil by using PC-SAFT equation of state

The precipitation tendency of heavy organics such as asphaltene has posed great challenges for petroleum industry, and thus study of asphaltene precipitation amount and formation conditions seems to be necessary. One of the most common approaches for prediction of asphaltene precipitation is using thermodynamic models. In this study a PC-SAFT equation of state (EOS) is used to predict asphaltene precipitation in two Iranian dead oil samples. Asphaltene content is obtained by filtration method of the oil samples diluted with specific concentrations of different normal alkanes. Also liquid-liquid equilibrium is used for characterization of oil sample into one heavy phase (asphaltene) and another light phase (saturates, aromatics, and resin). Calculations show that the developed model is highly sensitive to interaction parameter between oil fractions. Prediction results were improved due to using Chueh-Prausnitz equation. The results indicate good potential of PC-SAFT EOS in the prediction of asphaltene precipitation in crude oil samples diluted with different normal alkanes. The model error is <5% and the model precision is increased by reducing the number of normal alkane carbons.     

The Thermodynamic Modeling of Asphaltene Precipitation Equilibrium during the Natural Production of Crude Oil: The Role of Pressure and Temperature

Asphaltene precipitation is a sophisticated issue in the upstream oil industry, worldwide, and has detrimental effect on a verity of production processes; it damages the properties of the reservoir and causes an unfavorable and significant decrease in oil production. In spite of numerous studies to predict asphaltene behavior, the effect of temperature on asphaltene precipitation during pressure depletion at reservoir conditions is still obscure in the literature. In this study the PVT data as well as experimental data of asphaltene precipitation at reservoir conditions of an Iranian light oil samples is used, and the asphaltene precipitation and deposition envelops (APE and ADE) of the oil are developed using solid thermodynamic modeling.     

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.     

Study on the blockage in pores due to asphaltene precipitation during different CO2 flooding schemes with NMR technique

CO₂ flooding is an effective way in the tertiary oil recovery. While asphaltene often precipitates from the crude oil during the CO₂ flooding, and the mechanisms of blockage resulting from asphaltene precipitation is still unclear in different CO₂ flooding schemes. In this work, pure-CO₂ flooding, water-alternating-CO₂ flooding (WAG), and CO₂-foam flooding were applied to conduct the core-flooding experiments. Then, as for each flooding scheme, we quantitatively investigated the blockage degree in different pores due to asphaltene precipitation with nuclear magnetic resonance (NMR) technique. Tests results show that CO₂-foam flooding has a relatively higher blockage degree both in the smaller pores and the larger pores than WAG and pure-CO₂ flooding. Although pure-CO₂ flooding has the least asphaltene precipitation and blockage degree among three flooding schemes, its oil recovery degree is far less than the other two flooding schemes. Compared with pure-CO₂ flooding and CO₂-foam flooding, WAG flooding has the highest oil recovery and an acceptable asphaltene precipitation.     

气-液-固三相相平衡热力学模型预测石蜡沉积

在油气开采过程中,当体系的温度、压力或组成等热力学条件发生改变时,油气体系内的蜡质、胶质、沥青质等有机固相物质将会从体系中析出而沉积,给油气田生产带来严重的危害.采用状态方程和溶液理论相结合而建立了能模拟石蜡沉积的气液固三相相平衡热力学模型.根据正规溶液理论描述固相混合物的非理想性,采用状态方程描述气相和液相的相态.运用该模型对某一含气原油进行了蜡固相沉积模拟计算,计算结果表明,压力对蜡沉积有较大的影响,压力对蜡沉积点温度的影响在低于饱和压力下比高于饱和压力下的影响更为显著.     

Effect of pressure,temperature, and mass fraction of CO2 on the stability of the asphaltene constituents in crude oil

This paper focus on the main influence factors (temperature, pressure, and mass fraction of CO₂) on the state of asphaltene in the crude oil during CO₂ flooding by using high temperature and high pressure microanalysis system of solid precipitation. For the simulated oil sample – CO₂ system, the state of asphaltene is not affected by temperature within this range of 50°C to 100°C, the particle size of the asphaltene has an increase with the increase of the pressure from 8MPa to 40 MPa. When the mass fraction of CO₂ is less than 35%, the state of the asphaltene has not changed and the asphaltene particles are in a suspension state. When the mass fraction of CO₂ increases to 40%, the aggregation of the asphaltenes occurs and then form precipitation. With the further increase of the mass fraction of CO₂, the particle of the asphaltene aggregates has a significant increase. For the field development project design of CO₂ flooding, the influence of the temperature can be ignored, the appropriate mass fraction of CO₂ is below 35% and the gas injection pressure should maintain a relatively low value. The results can provide a theoretical basis to avoid the asphaltene precipitation during CO₂ flooding.     

Modeling of Asphaltene Deposition During Miscible CO2 Flooding

The authors present the results of numerical tests and simulations to investigate and analyze the likelihood of asphaltene precipitation and deposition during CO₂ flooding in a reservoir. The effects of asphaltene precipitation on oil properties such as oil viscosity and density during miscible CO₂ flooding process were elaborated by using Winprop software of Computer Modeling Group. Also oil properties change during CO₂ miscible flooding by numerical slim tube were investigated by a compositional simulator (GEM). A fluid sample of Saskatchewan Reservoir that had been flooded miscibly with CO₂ was chosen for performing the sensitivity analyses. The results showed that asphaltene precipitation reduces the oil viscosity and density that is in favor of production increasing. On the other hand asphaltene deposition causes resistance in oil production due to porosity and permeability reduction. The competition between these two effects declares the positive or negative effect of asphaltene on recovery that could be different for each reservoir. The results also show that decreasing the rate of CO₂ injection leads to an increase in asphaltene deposition near the injective well. Due to this phenomenon in higher injecting rates the increment in well bottom-hole pressure becomes less.     

Phase behavior and physical properties of CO2-saturated heavy oil and its constitutive fractions: Experimental data and correlations

An extensive set of phase behavior measurements were carried out on mixtures of carbon dioxide with a Canadian heavy oil and with its constitutive fractions. The heavy oil was divided into three fractions by asphaltene precipitation and distillation. The phase behavior data were then measured at 21°C and 140°C, and at several pressures up to 12.41 MPa, and included the mixtures' solubilities, swelling factors, densities, gas/oil ratios and viscosities. The oil samples obtained during the measurements were analyzed using gas chromatographic simulated distillation.The solubility of CO₂ increased with pressure and decreased with increasing temperature. Saturated mixture densities increased with pressure at 21°C; however, they decreased with pressure at 140°C. The extent of density change with pressure were small when compared to the changes due to temperature. A significant amount of oil swelling was also observed. An important effect of CO₂ was the large reduction in the oil viscosities. The extent of this reduction was larger at 21°C than at 140°C and was more pronounced for the more viscous oils. Simulated distillation analysis of the oil samples show the extraction of light ends into the CO₂ phase, but no deposition of heavy ends could be detected.The phase behavior data of the heavy oil and its fractions with CO₂ were correlated by the Peng-Robinson (PR) equation of state (EOS). The phase behavior data were also interpreted using binary and ternary mixtures of CO₂ with n- alkanes having the same molecular weights as the oil fractions. Mixture densities were correlated using the volume translated PR EOS and viscosities were correlated by equations proposed by Lederer.     

Influence of pressure and CO2 content on the asphaltene precipitation and oil recovery during CO2 flooding

During CO₂ flooding, the crude oil is treated with CO₂, and meanwhile it is displaced by CO₂. Based on the two processes, the influence of pressure and CO₂ content on the asphaltene precipitation and oil recovery efficiency are systematically investigated by indoor simulation experiment. With the increase of the pressure or CO₂ content during CO₂ treatment, the amount of asphaltene precipitation can be increased to a certain value. Correspondingly, the degrees of the changes of oil-water interface, the compositions of crude oil, and reservoir permeability are positively correlated with the amount of asphaltene precipitation. However, during the process, the oil recovery has an optimal value due to the combined action of asphaltene precipitation and the improvement of flow performance of the crude oil. These conclusions can provide a basis for high efficiency development of low permeability oil reservoirs by CO₂ flooding.     

CO2 miscible flooding in low permeability sandstone reservoirs and its influence on crude oil properties

Miscible CO₂ injection process has become widely used technique for the enhanced oil recovery in low permeability reservoirs. Core flooding experiments and field test of CO₂ miscible flooding in low permeability sandstone reservoirs and its influence on crude oil properties was studied. The results showed that CO₂ miscible flooding in low permeability sandstone reservoirs can enhance oil recovery both in laboratory study and field test. The permeability of sandstone reservoirs decreased during CO₂ miscible flooding due to the precipitation of asphaltene of crude oil. The precipitation of asphaltene lead to a reduction of asphaltene content and the apparent viscosity of crude oil. A further study on inhibitors and removers for asphaltene deposits from crude oil should be investigated to prevent and remove asphaltene deposits in low permeability sandstone reservoirs.     

The Prediction of Asphaltene Precipitation from Crude-Oils

Abstract

Asphaltene precipitation is undesirable deposition that causes difficult problems in oil production and transportation. A molecular thermodynamic model is proposed for predicting the asphaltene precipitation under live oil conditions and at a wide range of pressures and different solvent ratios. In this model, it is assumed that the precipitation phenomenon is a reversible process, and an equation of state is employed for phase behavior prediction. The vapor and liquid equilibrium calculations are performed separately and sequentially. The characterization of unknown-heavy fraction of petroleum (C₇₊) is obtained by the generalized molar mass distribution model, in which C₇₊ is represented by four pseudocomponents. The two heaviest pseudocomponents of C₇₊ are identified as asphaltenic components, are also considered as precipitating components. The model is verified by its ability to prediction of asphaltene precipitation in different thermodynamic conditions. It has been shown that the calculated results are in good agreement with the experimental data.