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.     

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.     

Effect of pressure,temperature, and mass fraction of CO2 on the state of the resin in crude oil

This paper focus on the main influence factors (temperature, pressure, and mass fraction of CO₂) on the state of resin in the crude oil during CO₂ flooding by using a visualization method. The state of resin is not affected by the variation of the temperature. Only when the pressure is increased to a certain value, the state of resin can be affected by the variation of the pressure. During the variation of the mass fraction of CO₂, the state of the resin has a significant change, including the growth out of nothing, expansion from small to large, and transformation from a adsorbed solid to a flowable liquid. During the actual application process of CO₂ flooding in oilfield, the influence of the temperature can be ignored, the appropriate mass fraction of CO₂ is below 30% and the gas injection pressure should maintain a relatively low value. The results can provide a theoretical basis to avoid the resin aggregation during CO₂ flooding.     

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.     

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.     

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 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.     

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%。     

Change of the chemical and physical properties of heavy oil before and after CO2 treatment

In order to improve the heavy oil displacement effect by CO₂ flooding, the change of the chemical and physical properties of heavy oil before and after CO₂ treatment is systematically investigated by indoor simulation experiment. Experimental results show that CO₂ treatment can decrease the amount of the saturates but increase that of the aromatics, and yet has little impact on those of resins and asphaltenes. Besides, the corresponding consequence is that there has an increase in the viscosity of the heavy oil and the particle size of the asphaltene micelle, and a decrease in the conductivity of the heavy oil and n-heptane systems and the stability of the asphaltene micelle after CO₂ treatment. The conclusions can provide a certain guidance for high-efficiency development of heavy oil reservoir by CO₂ flooding.     

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。     

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.     

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.     

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.     

Modeling CO2 miscible flooding for enhanced oil recovery

The injection of fuel-generated CO2 into oil reservoirs will lead to two benefits in both enhanced oil recovery (EOR) and the reduction in atmospheric emission of CO2. To get an insight into CO2 miscible flooding performance in oil reservoirs, a multi-compositional non-isothermal CO2 miscible flooding mathematical model is developed. The convection and diffusion of CO2-hydrocarbon mixtures in multiphase fluids in reservoirs, mass transfer between CO2 and crude, and formation damages caused by asphaltene precipitation are fully considered in the model. The governing equations are discretized in space using the integral finite difference method. The Newton-Raphson iterative technique was used to solve the nonlinear equation systems of mass and energy conservation. A numerical simulator, in which regular grids and irregular grids are optional, was developed for predicting CO2 miscible flooding processes. Two examples of one-dimensional (1D) regular and three-dimensional (3D) rectangle and polygonal grids are designed to demonstrate the functions of the simulator. Experimental data validate the developed simulator by comparison with 1D simulation results. The applications of the simulator indicate that it is feasible for predicting CO2 flooding in oil reservoirs for EOR.     

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.     

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.     

The effect of low-temperature oxidation in air-assisted steam flooding process for enhancing oil recovery

Air-assisted steam flooding is a new promoting technique for enhanced oil recovery compared to the other traditional thermal recovery methods. In this study, five experiments, including one steam flooding experiment, three combined steam–air flooding experiments, and one combined steam–N₂ flooding experiment were studied, under the conditions of 180 °C and back-pressure valve of 8 MPa, with sand-packed model. The volume fraction of mixed gas in these four combined steam–air (or N₂) flooding experiments were 80% steam+20% air, 60% steam+40% air, 40% steam+60% air, and 60% steam+40% N₂, respectively. The experimental results showed that air-assisted steam flooding could enhance the oil displacement efficiency when the volume fraction of air and steam was in a certain number, and the optimal condition is 60% steam+40% air. Furthermore, water cut curves and saturate, aromatic, resin, and asphaltene (SARA) analysis results also demonstrate that the low-temperature oxidation reaction in air-assisted steam flooding process advantageous to profile control of generating high viscosity “PLUG” to seal high-permeability channel in reservoir.     

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.     

The extraction effect of CO2 injection on the flow properties of crude oil

During CO₂ flooding, extraction of lighter hydrocarbons from crude oil makes the remaining oil hard to be recovered. In this work, we design a new experimental method to characterize the effect of CO₂ extraction on crude oil. The experimental results show that, the volume of extracted hydrocarbons increases as system pressure increases. The hydrocarbons with wider carbon number can be extracted from crude oil at high pressures. Moreover, the wax precipitation and viscosity of the remaining oil increase with increasing pressure. This study is expected to provide the basic understanding of the mechanisms of CO₂ flooding for enhanced oil recovery.     

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.