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.     

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.     

Changes in the properties of conventional crude oil before and after CO2 flooding

Abstract

In order to enhance oil recovery of a conventional oil reservoir by CO₂ flooding, the changes in the properties of the crude oil before and after CO₂ flooding are systematically investigated by on-site sampling and experimental testing. The results show that, after CO₂ flooding, the light hydrocarbons of the produced crude oil is increased and the heavy hydrocarbons of the produced crude oil is decreased due to the deposition of resins and asphaltenes in the pores of the formation. In addition, the produced fluid (a mixture of oil and water) has a high water separation rate, the oil- water interface has a high tension value, and the crude oil has a high acid value and a low viscosity. The conclusions can provide a certain guidance for high-efficiency development of a conventional oil reservoir 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.     

CO2驱酸化溶蚀作用对原油采收率的影响机理

CO₂驱酸化溶蚀作用对储层会产生一定程度的伤害。为揭示这种伤害作用对原油采收率的影响机理，选取6块同级别渗透率的岩心样品，在地层温度、压力条件下进行物理模拟实验，通过核磁共振技术评价酸化溶蚀作用对原油采收率的影响机理。实验结果显示，驱替产出流体的pH值低于原始地层水，且通过离子浓度变化发现驱替过程中有长石和碳酸盐矿物发生溶蚀；岩心的渗透率在驱替结束后出现一定程度降低，且反应时间越长，渗透率的降幅越大；岩心样品的最终采收率与反应时间呈反比，反应时间为240 h的岩心样品相比反应时间为0 h的岩心样品，其最终采收率降幅达到27.31%。综合分析认为，CO₂驱长时间的酸化溶蚀反应产物及脱落的黏土颗粒会堵塞孔喉，导致储层渗流能力下降，进而影响CO₂驱的驱油效率及最终采收率。     

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 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.     

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.     

Experimental study on asphaltene precipitation induced by CO2 flooding

The effects of CO2 pressure,temperature and concentration on asphaltene precipitation induced by CO2 were studied using a high-pressure vessel,interfacial tensiometer,Fourier transform infrared （FTIR） and drill core displacement experimental apparatus.The results indicated that the content of asphaltene in crude oil decreased,and the interfacial tension between a model oil and distilled water increased,with an increase of CO2 pressure,decrease of temperature and increase of molar ratio of CO2 to crude oil when CO2 contacted crude oil in the high pressure vessel.The content of asphaltene in sweepout oil and the permeability of test cores both also decreased with an increase of CO2 flooding pressure.The main reason for changes in content of asphaltene in crude oil,in interfacial tension between model oil and distilled water and in the permeability of the test core is the precipitation of asphaltene which is an interfacially active substance in crude oil.Precipitation of asphaltene also blocks pores in the drill core which decreases the permeability.     

CO2驱替过程中沥青质沉积及其对原油采收率的影响

针对CO2驱油过程中易造成沥青质等重有机质沉积,导致原油组分发生改变,影响驱油效果这一问题,考察了不同原油沥青质含量、岩心渗透率条件下沥青质的沉积量及CO2驱油效果,研究了CO2驱替过程中沥青质沉积和原油采收率的变化规律。实验结果表明,CO2驱油过程中引起的沥青质沉积与岩心渗透率、原油初始沥青质含量直接相关;相同条件下,低渗透岩心对沥青质沉积的影响更为明显;此外,随着沥青质沉积量的增加,CO2驱的采收率降低。     

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。     

Effect of nano titanium dioxide on heavy oil recovery during polymer flooding

In recent years, polymer flood of heavy oil has been extensively studied in laboratories and successfully applied in several fields. Polymer flooding is the most successful chemical enhanced oil recovery method. However, still, the need for a large amount of polymer, leading to high operational costs, presents a big challenge in technologies. This challenge can be addressed by considering the newly emerging nanomaterials. In this work, the author focuses on roles of TiO₂ nanoparticles on polymer viscosity and improve recovery in heavy oil recovery. He present the results obtained from a coreflood experiment with polymer injection in heavy oil at 1320 mPa.sec viscosity. Nanopolymer exhibits an outstanding flow behavior and enhanced oil recovery performance in coreflood displacement tests compared to base polymers. The results indicate that polymer flooding with higher viscosity can significantly improve oil recovery. Flooding test showed about 4% increase in oil recovery for nanopolymer solution in comparison with polymer solution after one pore volume fluid injection.     

聚合物驱后热化学沉淀调剖提高采收率技术研究

在探讨聚合物驱油后油层物性变化及剩余油分布特点的基础上,提出利用热化学沉淀进行油藏深部调剖提高采收率的方法。该方法的调剖原理不同于传统的调剖,主要通过缩小孔隙体积而达到降低高渗透层渗透率的目的。初步的物理模拟研究表明,选用硼酸钠溶液进行结晶沉淀,可以明显降低高渗透层的渗透率,且在10倍孔隙体积水洗后渗透率降低幅度仍可保持在55．8％～60．2％,并且“堵而不死”,实现真正意义上的调剖。在二维纵向非均质模型上的热化学沉淀调剖驱油实验表明,在聚合物驱后可继续提高采收率7．8％～9．2％,效果同于聚合物凝胶,并且具有注入粘度低、可进入残余油不连续分布的油藏深处等特点,尤其适合于温度适中的油藏。     

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,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.     

烃组分对CO2驱最小混相压力的影响

针对CO_2-EOR原油组分对混相能力影响的问题,应用界面张力消失法设计了不同碳数烃组分、不同族烃组分、不同含量烃组分混合模拟油与CO_2的最小混相压力实验,分析不同族烃组分与CO_2最小混相压力的变化规律,探寻原油中影响CO_2驱最小混相压力的关键组分。研究表明:原油中不同组分与CO_2的最小混相压力不同,相同碳数烃组分最小混相压力依次为:烷烃、环烷烃、芳香烃;同族烃的碳数越小,最小混相压力越小;相同碳数烃类的混合组分模拟油的最小混相压力小于单一烃组分的最小混相压力;原油中低碳数烷烃含量增加,最小混相压力降低,高碳数芳香烃含量增加,最小混相压力升高。该研究结果为多种类型油藏实施CO_2驱提高采收率提供了数据材料及理论支撑。     

非混相二氧化碳开采稠油

对埋藏深、油层薄、含油饱和度或孔隙度小的中等粘度稠油油藏来说，采用热采法开采不经济，需寻求一种开采效果比较好的非热采方法。该本通过对非混相二氧化碳开采稠油的室内研究和矿场试验的调研，证明非混相二氧化碳是开采这类稠油油藏的有效方法。     

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.     

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.     

中原油田CO2驱提高采收率技术及现场实践

系统总结了中原油田近十年来研究和实践形成的CO2驱提高采收率技术系列,包括CO2驱油机理、适宜性筛选评价技术、油藏工程技术和配套注采工程技术;评价分析了濮城沙一段下亚段油藏、胡96块等试验区的实施效果,总结不同类型油藏实施CO2驱的得失。研究结果表明,对于特高含水油藏,CO2溶于油斑和油膜,可驱动水驱残余油;对于深层低渗透油藏,CO2与原油界面张力小,毛管阻力小,可以驱替半径为0.01μm以上孔喉中原油。现场实践证实,CO2驱在防腐、剖面监测、分层注入及流度控制等方面已经形成了较成熟的技术,在深层低渗透油藏、特高含水油藏的应用中均取得了较好效果。同时,CO2驱具有不受温度、矿化度影响的优势,在高温高盐油藏具有巨大推广价值,为其他类型油藏注气提高采收率技术和实践提供借鉴。