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.     

超低界面张力泡沫体系界面性能

利用悬挂滴法和鼓气法,研究了发泡剂体系的界面性能和泡沫性能,考察了发泡剂体系中发泡剂(DWS)和聚合物(HPAM)浓度对界面张力、表面扩张模量及泡沫性能的影响。实验结果表明：发泡剂体系中DWS质量分数为0.1%～0.4%,HPAM浓度低于1500 mg/kg 时,与大庆原油可以形成超低界面张力。当发泡剂体系中HPAM浓度较大时,界面张力呈现增大趋势。DWS表面扩张模量随浓度增加而增加,在较低浓度出现极大值,且极大值处表面扩张模量值较大。发泡剂体系中加入HPAM有利于提高DWS的表面扩张模量。发泡剂体系的起泡性和稳泡性随DWS浓度增加而增强。发泡剂体系中HPAM浓度增加,泡沫稳定性增强,但其起泡性降低。     

疏水缔合聚合物在油水界面上的吸附行为

分别了研究了疏水缔合聚合物AP-P4不同相对分子质量时的油水界面张力、界面膜扩张模量、油水分配系数等界面性质,并利用双偏振光干涉技术研究了低相对分子质量AP-P4在不同原油组分油水界面的吸附行为,同时与HPAM进行了对比。实验发现:和HPAM不同,AP-P4能够降低油水界面张力,具有较强的乳化能力,同时能吸附在油水界面活性物质(沥青质和胶质)的表面,增强油水界面的扩张模量,从而增强聚驱采出液的稳定性。     

络合剂改善无碱一元和二元复合驱油体系的增粘能力和油水界面性能

通过研究络合剂对部分水解聚丙烯酰胺(HPAM)和直链烷基甜菜碱(BH)粘度和油水界面张力的影响,探讨了在高矿化度条件下,利用络合剂作为助剂改善无碱一元和二元复合驱油体系增粘能力和油水界面性能的方法。结果表明,在NaCl,CaCl2和MgCl2的质量浓度分别为6 500,890和520 mg/L的矿化水中,质量浓度为50 mg/L的络合剂就可以使质量浓度为1 800 mg/L的HPAM的粘度增加80%以上,可以使质量浓度为800~3 000 mg/L的直链烷基甜菜碱BH与原油的最低界面张力由10-2mN/m数量级降低到超低水平,而且这种络合剂也可以使1 800 mg/L HPAM—800 mg/L BH二元复合体系老化30 d的粘度增加40%以上,并使油水界面张力最低值由1.52×10-2mN/m降低到6.06×10-3mN/m。通过考察粘度和油水动态界面张力随不同老化时间的变化规律,分析了络合剂的作用机制。     

聚合物类型对油水界面性质影响研究

采用平面张力仪和表面粘弹性仪研究了部分水解聚丙烯酰胺（HPAM）和疏水缔合聚合物（HAP）对油水界面性质的影响研究结果表明,疏水缔合聚合物HAP可以显著降低煤油／模拟水体系界面张力,但对模拟油／模拟水体系界面张力影响较小;部分水解聚丙烯酰胺类聚合物CA对煤油／模拟水和模拟油／模拟水体系界面张力无明显影响。无论是煤油／模拟水体系还是模拟油／模拟水体系．随聚合物溶液浓度的增加,部分水解聚丙烯酰胺类聚合物CA均使体系界面剪切粘度逐渐增大。而疏水缔合聚合物HAP均使体系的界面剪切粘度先增加,后降低,而后再增加。部分水解聚丙烯酰胺（HPAM）相对分子质量较大时,HPAM溶液／模拟油体系的界面剪切粘度较大。     

缝洞型油藏剩余油形成机制及分布规律

采用钻孔和熔蜡的方法分别制备了缝洞油藏定量模型和随机模型,并用两种模型进行全直径岩心驱油实验,研究缝洞型油藏中剩余油形成机制及分布规律。研究结果表明:驱替相与被驱替相的密度差异和缝洞连接点位置决定溶洞中流体分布规律;一次水驱结束后剩余油包括油水密度差异形成的"阁楼油"、油水置换非瞬时性造成的"封存油"、溶洞不规则性造成的"角隅油"、缝洞复杂连接关系或者低连通度造成的"盲洞油"以及岩石润湿性造成的"油膜"。连接点位置越高,"阁楼油"含量越少;注入速度越低、原油黏度越小,"封存油"含量越少;溶洞形状越规则,角隅数量越少,"角隅油"含量越少;缝洞连接关系越简单、连通程度越高,"盲洞油"含量越少;水湿岩石表面"油膜"含量较少。     

新型表面活性聚合物驱油剂

从分子结构与性能关系入手,研发了具有低界面张力、可聚合的表面活性单体,将可聚合表面活性单体与丙烯酰胺进行共聚,采用复合引发体系、控制低温聚合的方法合成了一种新型表面活性聚合物驱油剂,并利用红外光谱、冷冻蚀刻电镜技术对其结构及其在溶液中的分布状态进行了表征。研究结果表明,可聚合表面活性单体与丙烯酰胺参与了接枝共聚,因而克服了色谱分离效应,新型表面活性聚合物驱油剂在不同水质中具有良好的水溶性、增黏性、耐温抗盐性与抗剪切性能,同时具有较低的油水界面张力,质量分数为0.15%的聚合物溶液与大庆采油一厂原油的界面张力达到1×10 1mN/m数量级。岩心驱油实验表明:新型表面活性聚合物驱油剂具有较好的增黏性及较低的油水界面张力,采收率较普通水解聚丙烯酰胺提高了5.2%。     

二元复合驱采出液的油水界面性质和破乳条件的关系

用界面张力仪和表面粘弹性仪研究了部分水解聚丙烯酰胺(HPAM)和表面活性剂(石油磺酸盐和非离子型表面活性剂)形成的二元复合体系对模拟油与模拟水(简称油水)界面特性、乳状液稳定性和采出液处理效果的影响。实验结果表明,含固体悬浮物的采出液过滤后与模拟油间的界面张力和界面剪切黏度降低;随表面活性剂浓度的增加,油水间的界面张力和界面剪切黏度降低,而随HPAM浓度的增加,油水间的界面张力和界面剪切黏度增加;原油与二元复合体系所形成的W/O和O/W型乳状液稳定性随HPAM和表面活性剂浓度的增加而提高;采出液中HPAM和表面活性剂的浓度增加,处理采出液的效果变差。     

复合驱体系化学剂静态损失评价方法研究

化学剂的损失程度直接影响化学段塞的使用效率。仅考察经油砂吸附后的化学剂损失,不能全面反映驱替过程中的化学剂静态损失程度。为此系统考察了三元复合驱体系经油砂和油相吸附后,表面活性剂质量分数和组成、NaOH质量分数及三元体系与原油间界面张力的变化。三元复合驱组成为:HPAM1.5g/L,表面活性剂上限质量分数0.3%,NaOH上限质量分数1.2%。实验结果表明,经油砂7次吸附后,表面活性剂质量分数从0.28%降至0.02%;NaOH质量分数从1.10%降至0.71%;三元体系经油砂5次吸附后,与原油间的界面张力已无法降至10^-3mN/m数量级。经油砂吸附后的三元体系与油相作用后,表面活性剂质量分数降低,最大降幅达50%,表面活性剂分子量明显升高;而NaOH质量分数降幅较小,最大降幅仅为15.22%;经油砂3次吸附后的三元体系与油相作用后,与原油间的界面张力已无法降至10^-3mN/m数量级。建议将油砂吸附与油相充分作用相结合,综合评价驱替液的化学剂静态损失程度。     

A correlation between interfacial tension,emulsifying ability and oil displacement efficiency of ASP system for Daqing crude oil

Abstract

Interfacial tension and emulsification are important to enhance oil recovery. There is almost none quantitative research on their correlation for Daqing crude oil. Experiments are performed to find out the correlation between different interfacial tension, emulsification and chemical flooding oil displacement efficiency. The authors changed the structure of surfactant to make characteristics of interfacial tension different significantly and build the relationship between interfacial tension parameters and chemical flooding oil displacement efficiency by physical simulate experiments. The ultralow interfacial tension index (expressed by S) is established by orthogonal test and actual significance of interfacial tension curves. The fitting formula between S and chemical flooding oil displacement efficiency (E) is: E = 0.856 ln(S) + 13.849. The emulsifying ability includes two aspects O/W and W/O. Authors changed the structure of surfactant to make characteristics of ASP systems have similar interfacial property but different emulsification property. Compared the oil displacement efficiency of these systems, built the correlation between emulsifying ability and chemical flooding oil displacement efficiency for Daqing crude oil.

This paper established the index of ultralow interfacial tension and emulsification, and summed up the formulae based on that with oil displacement efficiency. The quantitative evaluation of ASP system can optimize the existing evaluation methods and deepen understandings on flooding mechanism for Daqing crude oil.     

聚驱后缔合聚合物三元复合驱提高采收率技术

三元复合驱是大庆油田聚驱后进一步提高采收率的重要途径,其驱油体系须保证超低油-水界面张力,且能大幅提高波及能力。通过研究烷基苯磺酸盐（ABS）-缔合聚合物（HAPAM）-NaOH三元复合驱体系的性能,并与超高分子量部分水解聚丙烯酰胺（HPAM）三元复合体系进行对比。研究结果表明,HAPAM三元复合体系在NaOH浓度为0.5%~1.2%、ABS浓度为0.025%~0.300%时具有良好的界面活性,油-水界面张力可达10^-3mN/m数量级。0.16%HAPAM-0.3%ABS-1.2%NaOH三元复合体系黏度达108.8 mPa ·s,采用HPAM达到相同黏度其浓度为0.265%,因此HAPAM可降低聚合物用量40%。驱油实验结果表明,在相同黏度下,HAPAM三元复合体系在不同孔隙介质中均能提高聚驱后采收率13%以上,比HPAM三元复合体系多提高采收率6%以上。HAPAM三元复合体系具有更高的阻力系数与残余阻力系数、更好的黏弹性以及乳化稳定性,可以为大庆油田聚驱后提高采收率提供新的技术手段。     

烷基糖苷与重烷基苯磺酸盐复配体系性能研究

用质量比为1∶1的非离子表面活性剂烷基糖苷和阴离子表面活性剂重烷基苯磺酸盐的复配物,与部分水解聚丙烯酰胺组成了一种新型的二元复合驱油体系。室内实验研究结果表明:复配后的二元体系与大庆原油之间的界面张力值在45～80℃之间可达到超低,并且具有较好的抗盐和抗二价离子的性能;此二元复合体系在水驱后能进一步提高采收率,在聚驱后能进一步启动和驱替残余油。     

STUDY ON THE MICROEMULSION BEHAVIOR OF THE OXIDIZED PARAFFIN WAX

ABSTRACT

The interfacial tension between paraffin wax and water, as well as oxidized paraffin wax and water has been studied and the results showed that the interfacial tension between oxidized paraffin wax and water decreased obviously after paraffin wax was oxidized to proper degree. Meanwhile the pseudo-ternary phase diagram of the oxidized paraffin wax/surfactants/water system has been determined. It was confirmed that using a single surfactant A or cosurfactant B couldn't prepare oxidized paraffin wax microemulsion and the cosurfactant A/surfactant B mass ratio k _m has a proper range and an optimized value to produce the oxidized paraffin wax microemulsion, moreover, the microemulsion particle distribution was analyzed.     

Gemini Surfactant as a New “Green” Demulsifier for Treating Oilfield Emulsions

Abstract

Surface tension and interfacial tension (IFT) were the key factors asso- ciated with the stability of crude oil emulsion. Investigation of interfacial tension behavior related with the demulsification of crude oil emulsions can have a great impact on the development of crude oil demulsification processes and products. This article presents the surface and interface behaviors of Gemini surfactants (12-2-12, (12)-2-(12), (14)-2-(14)). The results indicated that (12)-2-(12) could exhibit higher surface and interface active properties. The demulsification efficiency and related factors were also discussed. It showed that as an environmentally friendly and safer demulsifier, Gemini surfactant could exhibit better demulsification efficiency.     

有机碱／HPAM二元复合驱体系的研究

针对吉林油田先导试验区现场试验中碱、部分水解聚丙烯酰胺（HPAM）、污水间配伍性差的问题,室内进行了新型有机碱／HPAM二元复合驱体系研究,确定其配方为：0．8％有机碱NPS-2＋1500—2500mg／LHPAM。性能评价结果表明,此二元复合驱体系可有效降低油水界面张力,与注入水配伍性好,室内驱油采收率比水驱提高17％以上。     

Dynamic Interfacial Tension Between Crude Oil and Novel Surfactant Flooding Systems Without Alkali

Abstract

The surface tensions of tetradecylmethylnaphthalene sulfonate (TMNS) surfactant aqueous solution and the dynamic interfacial tension (DIT) between crude oil, from Shandong Shengli oil field of China, and the surfactant solution without alkaline, was measured. Results indicate that the TMNS surfactant had great capability and efficiency of lowering the solution surface tension. The critical micelle concentration (cmc) is 0.001 mass% and the surface tension at this concentration is 28.19 mN.m^?1. It was also found that the TMNS surfactant is greatly effective in reducing the interfacial tensions and can lower the tension of crude oil-water interface to ultra-low at very low concentration, 0.002 mass%, without alkali and other additives. Both chromatogram separation of flooding and breakage of stratum are avoided effectively. The lower salinity is favorable for the flooding systems, lowering the DIT. The synthesized TMNS surfactant flooding systems without alkali and sodium chloride, decreasing the cost of oil recovery and avoiding the stratum being destroyed, would have a great prospect for enhanced oil recovery (EOR).     

Petroleum Sulfonates as Oil Displacement Agents and Application to Gudao Oil Field

Abstract

In terms of the condition of injection of water after polymer flooding of the Gudao oil field (Shengli, China), the following water quickly broke though the bank to the production wells, while most of residual oil remained in the formation. To solve the problem, two types of petroleum sulfonates made in China were selected to form an oil displacement agent (ODA) solution. The petroleum sulfonate available for crude oil from the Gudao oil field with the ultra-low interfacial tension can be found by drawing an oil/water interfacial tension contour diagram. The results show that the interfacial tension can be lower than 3.6 × 10^?4 mN/m when the active agent is contained with 0.25% Kelamayi petroleum sulfonate (KPS) + 0.225% Anqing petroleum sulfonate (APS) and if the agent reduces water resistance by entering the tiny pore to improve sweep coefficient and oil displacement efficiency. The polymer has no influence on the balanced value of interfacial tension but delays the interfacial tension to reach the balance. Pouring 0.3 pore volume (PV) high-efficient ODA into reservoir can improve 17% oil recovery (OR). Synergistic effects of two types of petroleum sulfonate with low cost to enhance OR will have an excellent prospect for enhanced oil recovery (EOR).     

二元复合驱表面活性剂在油水界面的作用机理

用介观模拟方法对二元复合驱用表面活性剂分子在油水界面的分布形态进行了研究。发现十二烷基苯磺酸钠（SDBS）和辛基苯基聚氧乙烯醚（TX100）均分布在油水的界面,单独使用时对界面张力的降低均有一个极值,但两者协同作用时呈互补的状态,使油水界面处表面活性剂分子的分布密度增大,更多地占据油水界面层,从而能够更多地降低界面的界面张力;聚丙烯酰胺（HPAM）不能降低界面张力,但自身能够通过分子链的缠结向四周延伸,形成一个空间网状结构,将周围的油滴连结起来,使油分子更容易聚集。     

Applying Grid partitioning based Fuzzy inference system method to estimate interfacial tension of brine and hydrocarbon

The oil recovery reservoirs and oil trapping in the reservoirs are extensively function of interfacial tension between brine and hydrocarbon, so estimation of interfacial tension becomes one of the interesting topics in petroleum industry. In this study, Grid partitioning based Fuzzy inference system method is utilized to forecast interfacial tension of hydrocarbon and brine based on various effective parameters such as ionic strength of brine, carbon number of hydrocarbon, pressure, and temperature. The estimated values of interfacial tension were compared with real interfacial tension of brine and hydrocarbon using graphical and statistical analyses. The determined coefficients of determination (R²) for training and testing phases were 0.9916 and 0.9447, respectively. The comparing analyses express that the Grid partitioning based Fuzzy inference system method has great ability in prediction of interfacial tension, and it can be used as an applicable tool in petroleum industry.     

Mechanism and Catalytic Behavior of Quaternary Ammonium Salts in Oxidative Desulfurization

Abstract

For the insolubility of binary phase system of oxidative desulfurization, quaternary ammonium salts as phase-transfer catalysts have been applied to enhance the reaction. To investigate the mechanism, nine catalytic systems were carried out. The results showed that the reaction was of pseudo-first-order in phase-transfer catalyst and substrate of organosulfur, and slightly influenced by the stirring rate documented the reaction was chemical controlled. In the oxidant anion [RCOOO^?] transfer process, there was an ion-pair [Q⁺ROOO^?] formed. To clarify the catalytic behavior of phase-transfer catalyst in the liquid-liquid phase system, oxidant anion transfer, interfacial tension and the activity of anion were exploited. It is shown that ion-pair [(C₄H₉)₄N⁺RCOOO^?] could be transferred from aqueous to organic phase, and catalyze the oxidative reaction best. Dibenzothiophene (with larger electrical density) was easier to be removed than thiophene, and the desulfurization rate of dibenzothiophene by tetrabutyl ammonium bisulfate was 97.45%. Some kinds of phase-transfer catalysts can reduce the interfacial tension to a proper value, therefore increasing the interfacial area and improving the rate of reaction. With greater distance separating cation from anion (0.317 nm) [(C₄H₉)₄N⁺RCOOO^?] was much easier to react with organosulfur than [RCOOOH].