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.     

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.     

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.     

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.     

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.     

Experimental Study of Asphaltene Deposition During Different Production Mechanisms

Abstract

Sudden changes in key parameters such as pressure, temperature, and fluid composition may result in asphaltene precipitation and deposition, consequently reducing permeability and porosity as well as well injectivity and productivity. Sandstone cores of an Iranian reservoir were studied under high pressure and temperature. Asphaltene deposition was studied in recycled gas injection, CO₂ injection, and natural depletion experiments. The authors observed that these processes could be ranked for the deposition severity viewpoint in the aforementioned order. Qualitatively investigation of cores indicated nonuniform deposition of precipitated asphaltene along a flooded core and reducing deposition from entering core terminal to the core outlet.     

Influence of injection pressure and injection volume of CO2 on asphaltene deposition

To further improve the oil displacement effect by CO₂ flooding, the trends and conditions of asphaltene deposition under different injection pressures and injection volumes of CO₂ were studied by SDS solid phase deposition testing system, high temperature and high pressure microscope, and P-X phase diagram. When the mole fraction of CO₂ in crude oil increases to a certain value, asphaltene deposition appears. The lower the pressure, the lower the mole fraction of CO₂ in crude oil causing the asphaltene deposition there is. After the onset of asphaltene deposition, the degree of deposition increases with an increase in pressure. The amount of the deposited asphaltene under miscible displacement is the highest, under near-miscible displacement is the second highest, and under immiscible displacement is the lowest. When the dissolution of CO₂ in crude oil reaches the saturation point, the asphaltene deposition becomes slow. Besides, it is feasible to prevent or reduce the asphaltene deposition by adjusting the thermodynamic parameters according to the phase behaviors of the CO₂-crude oil system. The experimental results can provide theoretical basis for optimization design of the parameters of 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.     

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.     

延长油田致密砂岩油藏CO2驱油机理研究

CO_2驱是提高低渗透油田产量、缓解温室效应的有效途径。针对鄂尔多斯盆地油藏压力系数低、原油轻质组分含量高的特点,通过PVT和最小混相压力等测试分析方法,揭示了低压、低孔、低渗油藏CO_2驱提高采收率主要机理。开展了CO_2注入储层与无机、有机物作用后的沉淀研究,表明CO_2在无机盐溶液中不会形成沉淀堵塞孔隙,CO_2与有机质作用后沉积点高于油藏压力,且注入压力越高,CO_2在地层原油中的溶解能力越强,目标区块CO_2注入后不易形成沥青质沉淀。物模驱替实验结果表明,均质岩心的采出程度明显高于非均质岩心,且随着岩心非均质性的增加,水驱采出程度、气驱采出程度及最终采出程度均明显下降。     

Simulation of Natural Depletion and Miscible Gas Injection Effects on Asphaltene Stability in Petroleum Reservoir Fluids

Abstract

Natural depletion of petroleum reservoirs as well as gas injection for enhance oil recovery, are unavoidable processes in the oil industry. Foremost, prediction of the problems due to these two processes is very necessary and important. So many field and experimental experiences have shown that heavy organic depositions, especially asphaltene deposition, are principal results during these processes. Results of laboratory simulation of asphaltene deposition during the natural depletion of petroleum reservoirs and also during gas injection and enhanced oil recovery (EOR) processes are reported here. This is achieved through the design of a new experimental setup for the investigation of pressure and composition effects on asphaltene deposition in petroleum fluids at high pressure and high temperature conditions. In this work, asphaltene deposition during decreasing pressure, from pressures greater than reservoir pressure to pressures below the bubble point pressure (natural depletion) and also asphaltene deposition during natural gas injection in reservoir conditions, are studied for three samples—one recombined sample and two bottomhole samples. All of the obtained results from this work conform to theoretical and other experimental works.     

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.     

CO_2注入过程中沥青质沉淀预测

注入CO2提高原油采收率过程中可能出现沥青质固相沉淀。鉴于沉淀沥青质的强极性,采用Anderko建立的缔合混合物状态方程描述沥青质的相行为,并由此推导沉淀沥青质组分的逸度计算公式,建立注气过程中气-液-沥青质三相相平衡数值计算模型。以某油田实际原油为例,利用模型计算了CO2注入过程中沥青质沉淀量,结果与实验数据相近,表明沥青质沉淀预测模型具有一定的准确性。在此基础上,预测了注气过程中沥青质沉淀变化规律:注入压力一定的情况下,沥青质沉淀量随着注入CO2量增加呈现先增加后减小的趋势,当CO2-原油体系中出现气相时,沥青质沉淀量达到最大;当CO2-原油体系中CO2物质的量分数一定时,在泡点压力附近沥青质沉淀量达到最大。图3表1参10     

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.     

注天然气油井沥青质析出规律研究

目的 解决东河区块原油在注气开采过程中沥青质沉积堵塞井筒问题。方法 采用高温高压固相沉积规律测试装置,基于光散射理论,研究了温度、压力、气油比等因素对沥青质析出特征的影响。结果 温度升高会增加沥青质在原油中的溶解度,促进原油稳定;等温降压过程中,沥青质随着压力降低逐渐析出,在泡点压力附近达到最大析出量,发生沥青质沉积堵塞油井的风险最大。DH-1井泡点压力对应井深2 140 m,与油井生产实际遇阻位置1 969 m接近,泡点压力可初步用于预测油井堵塞位置;溶解注气量越大,沥青质初始析出压力越大,沥青质析出压力区间也增大,沥青质沉积位置向油井深度下移。结论 研究揭示了注气过程沥青质的析出规律,对注天然气油井沥青质析出防治具有重要指导作用。     

Developing a Scaling Equation as a Function of Pressure and Temperature to Determine the Amount of Asphaltene Precipitation

A simple and applicable scaling equation as a function of pressure, temperature, molecular weight, dilution ratio (solvent), and weight percent of precipitated asphaltene has been developed. This equation can be used to determine the weight percent of precipitated asphaltene in the presence of difference precipitants (solvents) and the amount of solvent at onset point. Since increasing the pressure of crude oil decreases the amount of asphaltene precipitation, the effect of reservoir pressure has been taken into account in developing this equation. The results obtained by using this equation are substantially different and more accurate from other developed scaling equations for asphaltene precipitation. By considering the effect of reservoir pressure in developing the scaling equation and application of a genetic algorithm, the unknown parameters of the scaling equation are simultaneously and without any reservation obtained. The most important application of this unique equation is in the determination of critical point of asphaltene precipitation, known as onset point, and asphaltene precipitation in gas injection operations for enhanced oil recovery. The results predicted using the scaling equations are compared with the authors' experimental and literature precipitation data and it is shown that they are in good agreement with our experimental data. The scaling equation can be used in the design of gas-injected reservoir to prevent precipitation of the asphaltene aggregates in the reservoir.     

沥青质沉积对轻质油藏CO2驱的影响

为了解沥青质沉积对轻质油藏CO_2驱的影响,以CO_2及延长轻质原油为介质,在不同压力、不同CO_2与原油物质的量比的实验参数下,研究了CO_2对沥青质的沉积规律以及沥青质沉积对油水界面性质、原油组成、储层渗透率及采收率的影响。研究结果表明:当压力从0 Pa升至20 Pa时,沥青质沉积量从0.17%增至6.27%;沥青质沉积导致的储层渗透率损害程度从1.87%增至13.64%,油水界面张力原来的2.40 mN/m增至16.80 mN/m。压力在25 MPa时原油采收率最大,达到11.83%。     

Monitoring of asphaltene precipitation: Experimental and modeling study

Preparing relatively complete collections of experimental data on asphaltene precipitation in different reservoir conditions leads to considerable improvement in this area of science. In this work, asphaltene precipitation was studied upon two Iranian live oil samples, one a heavy oil and another light oil, under primary depletion as well as gas injections. Pressure depletion experiments were carried out at different temperatures to observe temperature effect besides pressure changes on asphaltene phase behavior. CO₂, dry and enriched gases were used as injecting agents to investigate the effect of different gases on asphaltene precipitation. Surprisingly, it was observed that raising temperature decreases the amount of precipitation in case of heavy oil while acting in favor of precipitation for light oil sample. In addition, Enriched gas resulted in more precipitation compared to dry one while CO₂ acted as hindering agent for light oil samples but increased the amount of precipitation in case of heavy oil. In the next part of this work, polydisperse thermodynamic model was developed by introducing an asphaltene molecular weight distribution function based on fractal aggregation. Modification that was introduced into polydisperse model not only solved the instability problem of Kawanaka model but also eliminates the need for resin concentration calculation. Flory–Huggins and Modified Flory–Huggins thermodynamic solubility models were applied to compare their predictions with proposed model.     

Simulation of Natural Depletion and Miscible Gas Injection Effects on Asphaltene Stability in Petroleum Reservoir Fluids

Natural depletion of petroleum reservoirs as well as gas injection for enhance oil recovery, are unavoidable processes in the oil industry. Foremost, prediction of the problems due to these two processes is very necessary and important. So many field and experimental experiences have shown that heavy organic depositions, especially asphaltene deposition, are principal results during these processes. Results of laboratory simulation of asphaltene deposition during the natural depletion of petroleum reservoirs and also during gas injection and enhanced oil recovery (EOR) processes are reported here. This is achieved through the design of a new experimental setup for the investigation of pressure and composition effects on asphaltene deposition in petroleum fluids at high pressure and high temperature conditions. In this work, asphaltene deposition during decreasing pressure, from pressures greater than reservoir pressure to pressures below the bubble point pressure (natural depletion) and also asphaltene deposition during natural gas injection in reservoir conditions, are studied for three samples—one recombined sample and two bottomhole samples. All of the obtained results from this work conform to theoretical and other experimental works.     

Asphaltene Deposition under CO2 Injection: An Experimental Study of the Bangestan Reservoir of Ahwaz Oilfield,SW Iran

Abstract

It is essential that precipitation of asphaltenes is recognized early in the planning stage of any CO₂ enhanced oil recovery (EOR) project so that appropriate testing can be performed to evaluate whether there will be a negative impact on reservoir performance. This article presents detailed evaluations of slim tube data that were obtained during CO₂ injection using a medium-gravity Iranian crude oil.

A crude oil from Bangestan reservoir of Ahwaz oilfield containing 18.2% asphaltenes with ~31.5 °API gravity was flooded by purified CO₂ (>96% CO₂) in a slim tube apparatus under 2,700 psi at 110°C. We were going to determine the minimum miscibility pressure (MMP) of the sample oil under injection of CO₂ flood, but when a CO₂ slim tube test was performed for this oil at 2,700 psi, less than half of the saturated oil in the tube was recovered, which implied that the displacement process was immiscible. At this pressure, the asphaltene deposition in the slim tube apparatus was so severe that even a pressure gradient of 6,200 lb/in² was not able to displace any fluid through the capillary tube. Therefore, we abandoned MMP determination with this sample and investigated the problem.

Due to the high percentage of asphaltenes in the sample, using the slim tube MMP as an apparatus for determining minimum miscibility pressure of CO₂ and sample oil can be misleading.