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.     

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.     

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.     

Oil recovery and CO2 storage in CO2 flooding

In this study, the interfacial tension (IFT) of crude oil-carbon dioxide mixtures was measured to determine the minimum miscibility pressure. CO₂ flooding with sand packs, long cores, and heterogeneous cores was conducted to investigate the oil recovery and storage efficiency. The experiment results show that the interfacial tension decreases linearly with increasing pressure at two different pressure ranges. Under immiscible condition, the oil recovery and storage efficiency are increased by 30.1% and 52.4% when the injection pressure is increased from 13 to 22 MPa, and improved by 16.3% and 22.04% when the permeability is decreased from 270 to 10 mD, respectively. Under miscible condition, increase of injection pressure can only lead to much slower increase of oil recovery and storage efficiency, and permeability almost has no influence on oil recovery and storage efficiency. The oil recovery and storage efficiency can be remarkably reduced by heterogeneity. Water alternating CO₂ injection can improve the oil recovery and storage efficiency by 35.5% and 13.55%, respectively, compared with continuous injection.     

高温高压条件下CO2 / 原油和N2 / 原油的界面张力

在油藏温度下,采用ADSA（axisymmetric drop shape analysis）技术测定了不同压力下CO₂/原油和N₂/原油体系的平衡界面张力。实验发现,原油与超临界CO₂接触的初始阶段存在强烈的扩散作用,原油中的轻质组分被超临界CO₂溶解抽提,并且随着压力的增加,这种溶解抽提作用增强;原油与N₂接触时,也存在相互扩散作用,但在本实验所测试的压力范围内（小于36 MPa）并不明显。两种体系的平衡界面张力随着压力的升高逐渐降低,其中CO₂/原油体系的平衡界面张力降低的幅度明显大于N₂/原油体系;N₂/原油体系的平衡界面张力随压力基本呈线性变化。在CO₂/原油体系中,当压力低于17.7MPa时,平衡界面张力下降非常快;当压力大于17. MPa时,CO₂/原油体系的平衡界面张力下降较慢。     

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.     

Modeling crude oil gasification

Abstract

The characteristics of CO₂-gasification of crude oil under steady-state condition were studied using a simulator. The model was developed using the minimization Gibbs free energy minimization. The effects of reactor temperature and CO₂/crude oil ratio on gas composition and lower heating value (LHV) of the produced syngas were investigated. As a result, the maximum LHV was obtained at a CO₂/crude oil ratio of 0.1 and gasification temperature of 800?°C.     

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.     

模拟延长油田CO_2驱油过程原油结蜡特性研究

通过对某CO2驱油区块的不同CO2分压条件下原油结蜡倾向和原油结蜡特性评价,计算出原油的结蜡速率、结蜡率及蜡含量,分析了原油的析蜡曲线特性。结果表明,CO2分压增大时原油的结蜡速率和结蜡率提高,蜡含量降低,蜡析出更明显;经CO2处理作用后原油析蜡点向低温方向移动,其蜡含量也相应地比未处理油样的蜡含量降低。     

原油组成对碱-表面活性剂-聚合物三元复合驱的影响

采用大庆油田不同区域油水样与碱-表面活性剂-聚合物(ASP)三元复合体系相互作用,研究了原油组成对三元复合驱增油效果及采出液性质的影响;采用FTIR,GC-MS,XRF等方法对原油油水样、萃取活性组分、萃余油组分及油相中硫元素含量进行表征。表征结果显示,各油水样中的萃取活性组分均具有典型一元饱和羧酸(脂肪酸和环烷酸)峰值特征,喇嘛甸油水样萃余油正构烷烃中的重质组分含量较高,其组成与表面活性剂重烷基苯磺酸盐的组分更接近。实验结果表明,油水样中萃取活性组分及萃余油与三元复合体系间界面张力虽较高,但原油与三元复合体系间却可实现超低界面张力。     

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.     

High energy and low emissions from catalytic combustion of crude oil

Combustion technology has been investigated to effectively and economically heat and power generation. A kinetic model of crude oil combustion in presence of CaO as a catalyst was developed. Effects of CaO mass yield (ppm) on three main parameters including combustion carbon conversion efficiency, reaction temperature, and combustion efficiency were investigated. Results showed that the CaO has a significant effect on the decrease of CO₂, which is the most important greenhouse gas. It also found that the carbon conversion efficiency decreases as the CaO increases, although it is not considerable.     

非均质多层储层中CO2驱替方式对驱油效果及储层伤害的影响

低渗透油藏注CO₂开发过程中沥青质沉淀和CO₂-地层水-岩石相互作用引起的储层堵塞加剧了非均质多层砂岩储层中驱替特征的复杂性，影响CO₂和CO₂-水交替驱（CO₂-WAG）驱油过程中流体在储层中的渗流和最终的原油采收率。研究中的CO₂和CO₂-WAG驱油实验是在混相条件下（70℃、18 MPa）模拟的具有相似物性的多层储层系统中进行的，从油气产量、剩余油分布和渗透率损害3方面评价了两种驱替方式。实验结果表明，CO₂驱后整个系统的采收率较低，产油主要来自高渗透层，剩余油分布在中、低渗透层。CO₂-WAG驱过程中CO₂突破时间较晚，整个系统的原油采收率显著改善。此外，CO₂驱后高渗透层的渗透率下降了16.1%，95.1%的下降幅度是由沥青质沉淀引起。在CO₂-WAG驱后，各层的渗透率下降幅度分别为29.4%、16.8%和6.9%，沥青质沉淀仍是主要因素，且引起的储层堵塞更严重，但高渗透层中CO₂-地层水-岩石相互作用引起的渗透率下降不容忽视，占20.7%的因素。因此，对于具有强非均质性的多层储层，CO₂-WAG具有更好的驱油效果，但是对沥青质沉淀的预防和控制措施是必要的。     

Experimental Investigation of Miscible CO2 Flooding

Abstract

Management of water alternating gas (WAG) injection projects requires making decisions regarding the WAG ratio, half-cycle-slug size, and ultimate solvent slug size. The impact of these decisions affects the capital cost and ultimate incremental oil recovery. Core flooding runs were conducted on 2 and 4 ft core samples. Injection scheme (continuous gas injection [CGI] vs. WAG), WAG ratio, and slug size were investigated. In addition, miscible WAG flooding as a secondary process was investigated and its efficiency was compared to the conventional tertiary miscible gas flooding. Miscible gas flooding at different miscible WAG parameters (WAG ratio and slug size) indicate that 1:2 WAG ratio at 0.2 PV slug size is the best combination yielding the highest recovery and tertiary recovery factors. Miscible WAG flooding as a secondary process indicated a higher ultimate recovery compared to the conventional tertiary WAG flooding. However, a larger amount of gas injection is consumed particularly in the early stages of the injection process. Miscible CGI mode conducted using n-Decane as oleic phase appears to have better performance than miscible WAG injection in term of recovery. When light Arab crude oil was used as oleic phase, higher recovery was obtained for miscible WAG flooding. The reversal trend seen in is believed to be due to the presence of crude oil, which alters the rock wettability toward an oil-wet condition, preventing the water blockage during the WAG process.     

普通稠油化学驱油技术现状及发展趋势

对于普通稠油,一次采油后常采用注水开发和热采方法。据中石化2007年底统计,采用注水开发动用的普通稠油储量占稠油总储量的30.1%,但由于水油流度比高,使得普通稠油油藏水驱采收率低。当油层太薄或埋藏太深时,热量损失严重,经济上不适合采用热采方法。化学驱方法是一个重要的接替手段。因此,文中重点综述了聚合物驱、碱驱、碱/表面活性剂驱、碱/聚合物驱技术在普通稠油油藏中应用的国内外研究现状和机理研究进展,指出了稠油化学驱中出现的问题和未来的发展趋势。     

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.     

CO_2驱后储层及剩余油物性变化探讨

目前对注CO2提高原油采收率相关问题研究已经比较深入,而对CO2驱后储层及剩余油物性变化的研究还不多。据统计,成功进行CO2驱后剩余油饱和度约30%,为进一步提高原油采收率,研究CO2驱后储层及剩余油物性的变化是非常必要的,主要从以下三个方面进行分析：CO2驱后储层物性变化、CO2驱后剩余油物性的变化及剩余油与储层之间的关系变化。     

低渗油藏水驱后CO2潜力评价及注采方式优选

针对延长油田乔家洼区块由于基质致密和非均质性严重造成注水开发效果差的问题,通过开展CO2室内驱油实验,在水驱基础上分别对连续气驱和气水交替驱驱油潜力进行评价,并对气水交替驱流体注入速度、段塞尺寸及气水比等注入参数进行优化。同时,对区块采用水驱、优化井网后水驱、利用优化的CO2驱注入参数开展气驱和注气5年后转气水交替驱4种开发方案,进行数值模拟产量预测。实验结果表明,CO2驱在目标区块高含水后有着较大驱油潜力,连续气驱和气水交替驱分别在水驱基础上可提高采收率8.43%和20.95%;气水交替注入方式下采收率随各注入参数的增大均呈先增加后降低的趋势,最佳注入速度、最佳注入段塞尺寸和最佳气水比分别为0.73mL/min、0.1PV和1∶1。数值模拟结果表明:优化井网后水驱、连续气驱和注气5年后转气水交替驱3种方案在开发15年后,分别可以在原水驱方案基础上提高采收率0.77%、13.81%和12.98%,建议采用注气5年后转气水交替驱方案进行生产。     

Operation Parameters on CO2-Foam process

Abstract

Reducing the mobility of CO₂ by means of generating in situ foam is an effective method for improving the oil recovery in CO₂ flooding processes. Implementation of the CO₂-foam technique typically involves the co-injection of CO₂ and surfactant solution into the porous medium. The surfactant molecules form bubble films that trap the flowing CO₂ molecules. The effectiveness of the CO₂-foam process is measured in terms of foam mobility. The mobility of CO₂-foam is affected by different operation parameters, such as pressure, temperature, foam quality, and brine concentration. However, surfactant type governs the overall efficiency of the CO₂-foam process. This paper presents the results of a series of experiments conducted to study the effect of various parameters on the CO₂-foam process. Bottle tests were conducted for four commercially available surfactants and among them, Chaser CD-1045 was found to be the most effective surfactant for CO₂-foam flow under reservoir conditions. It was observed that an increase in pressure from 1, 200 psi to 1, 500 psi leads to increase of the mobility of CO₂-foam, and an increase in temperature from 72 to 122°F reduces the mobility. Also, as the foam quality increases from 20 to 80%, the mobility decreases. It was observed that there was no significant effect on the mobility with an increase in brine concentration from 1 to 3 wt%.     

The Effects of Miscible CO2 Injection on Oil Biomarker Parameters

The purpose of this research was to study the effect of CO₂ injection on the geochemistry of crude oil in order to determine the probability of using geochemical parameters for monitoring CO₂ injection. In this process, four oil samples from different offshore oil fields were collected, synthetic steady state oil reservoir (porous media) were made by slim tube apparatus, then CO₂ injection process was done in different pressures. Various geochemical analyses were also carried out on the injected oil before and after the injection. The results show that the bulky changes on oil sample by CO₂ injection. CO₂ injection is more likely to precipitate complex and large molecules such as asphaltenes-resins and also large normal alkanes. In this case, the percentage of aromatic molecules was increased during injection. In general view on chromatograms, the height and abundance of all saturated compound peaks after CO₂ injection were significantly decreased. However, biomarker analysis shows that CO₂ injection has a tendency to change source and maturity biomarker parameters.