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.     

低渗油藏CO_2驱油混相条件的探讨

CO2与地层油能否达到混相状态对CO2驱油技术的应用效果有重要影响,界面张力法和细管实验法测量的最小混相压力(MMP)存在较大差异。岩心孔隙结构对原油相对体积及CO2密度的影响实验均说明,多孔介质的孔隙特征对流体物性参数产生较大影响,用细管实验MMP值作为油藏条件下CO2-原油体系MMP值的做法也需要理论完善。对影响CO2驱油混相条件的主要因素进行分析,认为岩石孔隙特征、地层压力以及注入流量对多孔介质中CO2-原油体系MMP有明显影响。渗透率下降,测量的MMP值也不同程度地降低;相对而言,平均地层压力较低的油藏,测量的MMP值也较低;对注入流量的研究认为优化流量可获得较低的MMP值。综合分析以上3个因素,初步建立计算多孔介质中CO2-原油体系MMP的方程。该研究将压力分布曲线进一步细化,补充了对不同压力间流体状态的描述。图7表1参11     

CO_2细管模型驱油效果研究

鉴于气驱技术对开发低渗透油藏的良好效果,运用了目前最可靠的测量最小混相压力的细管实验方法,进行了对CO2气体与原油最小混相压力的预测研究.详述了细管实验的实验条件、实验方法、具体步骤与原理.分析结果得到了注采压差、采油速度和采收率随驱替压力的变化规律,并测量了原油与CO2作用的最小混相压力,给出了合理的驱替压力范围,为油藏开采提供了参考依据.     

低渗透砂岩油藏渗吸采油影响因素研究

通过对低渗透砂岩应用静态渗吸实验方法,研究界面张力、渗透率、原油黏度、渗吸液矿化度对渗吸过程的影响规律,认识不同因素对渗吸采油效率的影响。结合渗吸机理,通过渗吸速度、渗吸采收率的比较,发现一定范围内,界面张力为10-1mN/m数量级、较高渗透率、较低原油黏度、较高渗吸液矿化度条件下,表现出较好的渗吸效果。     

超低渗透油藏CO2驱最小混相压力实验

利用常规方法测量超低渗透油藏CO₂-原油最小混相压力时,存在测量周期长、工作量大等问题,且不能直接观察到CO₂与原油的混相状态。为了确定杏河超低渗透油藏CO₂-原油的最小混相压力,采用界面张力法对杏河油藏CO₂和原油进行室内实验。结果表明：随着平衡压力的升高,原油中溶解CO₂的量增多, CO₂-原油之间界面张力的变化可分为2个阶段,且均呈逐渐减小的线性关系;当平衡压力从4 MPa增大到28 MPa时, CO₂-原油之间的界面张力由17.72 mN/m降到1.56 mN/m。界面张力法测得杏河油藏最小混相压力值为22.5 MPa,略大于细管实验测得的最小混相压力值22.3 MPa,由于二者数值相差仅0.9%,表明界面张力法测量超低渗透油藏最小混相压力具有较好的准确性。通过上述研究,确定了杏河油藏最小混相压力,为杏河油藏注CO₂增产开发方案的制定提供了理论支持,但是由于最小混相压力高于油藏目前压力（17.5 MPa）,在目前油藏条件下CO₂与原油不能实现混相。     

Mechanism of the viscosity reduction with ternary compound in the sulfonate-straight chain alcohol-alkaline compound system

Research shows that the viscosity greatly reduction of viscous crude oil can improve the exploitation and promote the fluidity. We studied the effects and the mechanism of viscosity reduction of viscous crude oil emulsion after introducing the ternary compound of sulfonate-straight chain alcohol-alkaline as the viscosity reducer. Results showed that the best emulsifying performance can be achieved using 5% 1-pentanol. 0.2% of Na₂CO₃ and DEA shows the strongest emulsification ability of the O/W emulsion. The use of AOS, straight chain alcohol and petroleum carboxylate resolves diffusion on the oil-water interface, which can form a dense surfactant of single molecular layer to reduce the interfacial tension and prevent the phase change of the emulsification. When the mass fraction of AOS, Na₂CO₃, DEA and 1-pentanol were 0.2%, 0.25%, 0.2% and 5% respectively, the viscous crude oil would achieve the best effect of viscosity reduction.     

特低渗砂岩油藏CO2-低界面张力黏弹流体协同驱油机理研究

目的特低渗油藏储层物性差、层间非均质性强,造成CO₂驱易发生气窜,提高采收率效果欠佳,其中,CO₂水气交替驱作为结合CO₂驱和水驱优势的方法,具有较高的适用性。为进一步改善CO₂-水交替驱的开发效果,开展了CO₂-低界面张力黏弹流体协同驱油研究。 方法通过界面张力和润湿性能测试评价低界面张力黏弹流体基本性能,并利用微观可视化驱油实验及岩心驱油实验等,探究了不同驱替方式的驱油效果和CO₂-低界面张力黏弹流体协同驱油过程中二者之间的“协同作用”机理。 结果低界面张力黏弹流体具备良好的界面活性和改变岩石表面润湿性能力,水驱后开展CO₂驱、低界面张力黏弹流体驱、CO₂-低界面张力黏弹流体交替协同驱,采收率可在水驱基础上分别提高0.91%、10.66%、16.25%,其提高采收率机理包括降低界面张力、改善流度比、改变岩石表面润湿性及乳化作用的协同效应等。 结论CO₂-低界面张力黏弹流体协同驱既可有效增强非均质特低渗砂岩油藏注CO₂过程中气体流动性控制,又能够降低CO₂萃取轻烃导致重质组分沉积的影响,具有协同增效作用。      

Study on emulsification of crude oil in water using emulsan biosurfactant for pipeline transportation

In this work, an experimental investigation on removing crude oil from a stainless steel tube using a biosurfactant such as emulsan was studied. The emulsan used in this study was produced by Acinetobacter calcoaceticus PTCC1318. The produced emulsan was able to reduce the surface and interfacial tension of water to 24 mN/m and 3 mN/m, respectively. Also influence of water- oil ratio on emulsifying property was studied. The results showed at CMC concentration, emulsification index (E₂₄) of emulsions decreased with increasing water- oil ratio. At 25°C, 30 mg/L, with a water–oil ratio of 1:2, produced emulsan formed an excellent emulsification of crude oil about 98%. Cleaning parameters tested included washing time and flow rate. It also demonstrated that the emulsan is useful for the tube cleaning with removal percentages of 100% at the room temperature, depending on the washing conditions.     

压裂液存留液对致密油储层渗吸替油效果的影响

统计长庆油田罗*区块2015年存地液量与油井一年累积产量的关系发现,存地液量越大,一年累积产量越高,与常规的返排率越高产量越高概念恰恰相反,可能与存地液的自发渗吸替油有关。核磁实验结果表明,渗吸替油不同于驱替作用,渗吸过程中小孔隙对采出程度贡献大,而驱替过程中大孔隙对采出程度贡献大,但从现场致密储层岩心孔隙度来看,储层驱替效果明显弱于渗吸效果。通过实验研究了影响自发渗吸效率因素,探索影响压裂液油水置换的关键影响因素,得出了最佳渗吸采出率及最大渗吸速度现场参数。结果表明,各参数对渗吸速度的影响顺序为:界面张力 > 渗透率 > 原油黏度 > 矿化度,岩心渗透率越大,渗吸采收率越大,但是增幅逐渐减小;原油黏度越小,渗吸采收率越大;渗吸液矿化度越大,渗吸采收率越大;当渗吸液中助排剂浓度在0.005%~5%,即界面张力在0.316~10.815 mN/m范围内时,浓度为0.5%（界面张力为0.869 mN/m）的渗吸液可以使渗吸采收率达到最大。静态渗吸结果表明:并不是界面张力越低,采收率越高,而是存在某一最佳界面张力,使地层中被绕流油的数量减少,渗吸采收率达到最高,为油田提高致密储层采收率提供实验指导。      

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.     

Interfacial Interactions Between Crude Oil and CO2 Under Reservoir Conditions

Abstract

In this paper, an experimental technique was developed to study the interfacial interactions between crude oil and CO₂ under reservoir conditions. By using the axisymmetric drop shape analysis (ADSA) for the pendant drop case, this new technique makes it possible to measure the interfacial tensions (IFTs) between crude oil and solvents, such as CO₂, at high pressures and elevated temperatures. The major component of this experimental setup is a see-through windowed high-pressure cell. In this study, the IFT of the crude-oil–CO₂ system was measured as a function of pressure at two fixed temperatures. It was found that, due to mutual interfacial interactions between crude oil and CO₂, their dynamic IFT gradually reduces to a constant value, i.e., the equilibrium IFT. The major interfacial interactions observed in this study include light-ends extraction and initial turbulent mixing. At T = 58°C, the equilibrium IFT reaches 1–2 dyne/cm when P ≥ 13.362 MPa, and only partial miscibility is achieved even up to P = 28.310 MPa. Thus, this experimental study shows that only partial miscibility can be obtained in most CO₂ flooding reservoirs. In addition, it is expected that the observed light-ends extraction and initial turbulent mixing phenomena may have significant effects on ultimate oil recovery and long-term CO₂ sequestration.     

Use of oil-soluble surfactant to reduce minimum miscibility pressure

In some low-permeable reservoirs, the miscibility pressure is far higher than the formation pressure, which makes it not feasible to have a CO₂ miscible displacement. In this study, an oil-soluble surfactant, CAE, was designed and synthesized to reduce interfacial tension (IFT) and CO₂-oil minimum miscible pressure (MMP), making it possible to release miscible displacement increasing oil recover. Experiment results showed that oil soluble surfactant can be dissolved in supercritical CO₂ but not soluble in water. It is also found that the CAE preslug displacement has the higher displacement efficiency than displacement with the CAE dissolved in CO₂. Based on a series of CAE preslug displacement experiments with varying CAE concentrations, the optimal injection concentration of CAE is 0.2%. Moreover the MMP determined under the CAE concentration of 0.2% is 6.1 MPa lower than that of pure CO₂ displacement. It reduces the MMP more than liquid gas preslug displacement (3.2 MPa) when the same volume of liquid gas is used with the CAE used in CAE preslug displacement test.     

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.     

Evaluation of Interfacial Tension Between Zahra Oil and ASP Solution

Alkaline-surfactant-polymer (ASP) flooding has been proved to be an effective enhanced oil recovery (EOR) method. Reduction of interfacial tension (IFT) between crude oil and ASP solution is the main mechanism in ASP flooding. Evaluating IFT between crude oil and ASP solution is a key parameter for ASP flooding in laboratory experiments or field projects. In order to obtain good result of ASP flooding in the reservoir in Zahra field, the influence of the concentration of Na₂CO₃ on IFT between Zahra crude oil and ASP solution with three different surfactants, BHJC, SS-231, and SS-233, was researched. IFT was measured with surface tension meter SVT20N, Dataphysics Co. Germany, at 72°C. For the view of IFT result anionic surfactant BHJC is more suitable for the Zahra oil field. This research is helpful for practical application of ASP flooding in Zahra oil field.     

Dynamic Interfacial Tension Between Gudao Heavy Oil and Petroleum Sulfonate/HPAM Complex Systems

Abstract

The dynamic interfacial tension between Gudao heavy oil and petroleum sulfonate/hydrolyzed polyacrylamide complex system was studied. It is shown that with the addition of hydrolyzed polyacrylamide into the solution of petroleum sulfonate, not only is the viscosity of the complex system increased, but also the dynamic interfacial tension is further lowered. Thus a complex system with high viscosity and low interfacial tension can be constituted by 0.3 wt% petroleum sulfonate and 0.18 wt% hydrolyzed polyacrylamide with a viscosity-averaged molecular weight of 1 × 10⁷. In addition, the dynamic interfacial tension between complex system and crude oil can also be lowered by increasing the salt content in solution.     

微乳助排剂的研制及性能评价

采用两性表面活性剂、双子表面活性剂和非离子表面活性剂作为主剂、添加助剂及油相,复配得到了具有低表面张力和低界面张力的微乳液,并对其粒径、热稳定性、改善水润湿性能力、与压裂液配伍性及返排提高率进行评价,得到了具有优异助排效果的微乳液体系。结果表明:该体系粒径分布约80nm,其表面张力平衡值约26.0mN/m,与煤油间界面张力最低可降至0.1mN/m,可改善云母表面润湿性,与其接触角最高改善约70°,返排提高率最高达到了29.72%;微乳液具有一定的耐温性,且与压裂液、添加剂和破胶液配伍性良好。     

延长油田含油污泥处理现场试验研究

重新回收温室气体CO2注入地层原油进行混相驱油是实现CO2封存和利用的主要途径之一,但其最小混相压力（MMP）被认为是该技术的一个关键参数。采用悬滴法测定了CO2和4种不同地层原油之间的界面张力,并直观地确定了4种不同地层原油注CO2驱油的MMP分别为：24.12MPa、24.81MPa、26.87 MPa和31.69 MPa。同时,采用多项式外延法确定各自的MMP,对比发现外延法确定的MMP误差均在3.0%以内,且MMP越高,误差越小。该实验表明,采用界面消失技术确定MMP具有操作简单、耗时少、成本低、准确度高等特点。     

Characterization of ternary compound viscosity reducer system on viscosity of viscous crude oil

Based on the theory that viscous crude oil can form stable two-phase oil-water interfacial molecular membrane with surfactant, the oil-water interfacial activity and viscosity reduction of oil-water interface of viscous crude oil were studied for the ternary compound system, including anionic surfactant alpha olefin sulfonate (AOS), weak alkali Na₂CO₃ and four different kinds of nonionic surfactant emulsifying silicon oil (LKR-1023), lauryl diethanolamide (LDEA), isomeric alcohol ethoxylates (E-1306), and polyoxyethylene sorbitan monooleate (T-80). Results showed when lipophilic or hydrophilic nonionic surfactants were used separately in the same compound system. The viscosity of viscous crude oil could be reduced, but the viscosity reduction efficacy was not desirable. However, using LKR-1023, E-1306, and T-80 as nonionic surfactant with mass fraction 1.0%, the viscosity reduction rate of viscous crude oil reaches 98.92%, 98.29%, and 96.87%, respectively. With 1.4% of LDEA, the viscosity reduction rate of viscous crude oil can reach 98.89%. Through all different kinds of the nonionic surfactant tested, oil-in-water (O/W) emulsion under LDEA ternary compound system has been proved to be the most stable with no phase inversion. Therefore, it is promising to improve the viscosity reduction of the super viscous crude oil by selecting the proper surfactant and dosage.     

Experimental investigation of interfacial tension and oil swelling for asphaltenic crude oil/carbonated water system

The phenomenon of oil swelling at the oil-carbonated water (CW) system could be an important mechanism during the water alternating gas (WAG) injection process. Nevertheless, the study of the main mechanisms during water flooding (WF) is a complex topic that has not been well revealed so far, especially for asphaltenic crude oil (ACO) systems. Hence, the main goal of this experimental work is to determine the influence of carbon dioxide (CO₂) within the water phase in the interfacial tension (IFT) between water and crude oil for an extensive range of pressures between 400 psi and 2000 psi (i.e. 2.76–13.79 MPa), under two temperatures of 313.15 and 323.15 K (i.e. 40 and 50 °C) by axisymmetric drop shape analysis (ADSA) method. The experimental results demonstrate that the water/ CW and crude oil IFTs decline with time. The value of dynamic IFT (DIFT) between CW and crude oil decreased about 6 mN/m in comparison with the oil–water DIFT. As a result of the CO₂ solubility, the crude oil droplet swells with increasing pressure. When the temperature rises, the effects of increasing entropy phenomena and decline of liquids density is dominant compared to the solubility of CO₂. Thus, the volume of oil droplet increases with temperature, unexpectedly. In addition, as thetemperature increases the water/CW-Oil IFT is slightly reduced over a wide range of pressure evaluated. Nevertheless, there is a slight increase as the pressure increases for the water–oil system. According to the predicted results, interfacial tension of the CW-oil system declines with increasing pressure until the solubility of CO₂ is reached to a maximum value and then approximately remains changeless.     

Na+质量浓度对三元复合体系的影响

 阳离子对三元复合体系(表面活性剂+聚合物+NaOH,alkaline/surfactant/polymer,简称ASP)的性能影响较大。在纯水配制的三元复合体系中,利用NaOH和NaCl的质量分数来调节其中Na⁺的质量浓度,考察三元复合体系中Na⁺质量浓度对体系黏度及其与原油之间油-水界面张力的影响。结果表明,三元复合体系中Na⁺质量浓度达到较高值时,三元复合体系黏度就不再变化。在三元复合体系中,无论是NaOH质量分数高而NaCl质量分数低,还是NaCl质量分数高而NaOH质量分数低,只要体系中Na⁺质量浓度在5200~7700 mg/L,就能与原油形成超低油 水界面张力,这是三元复合体系Na⁺质量浓度的变化导致表面活性剂分子在油-水界面上的吸附发生变化的结果。