混合烷基苯磺酸盐的制备、评价及分析

三次采油需要大量的高性价比磺酸盐类表面活性剂。以炼油厂馏分油为主要原料,AlCl3为催化剂合成混合烷基苯,再与发烟硫酸反应制备混合烷基苯磺酸盐,并评价合成样品的综合性能。结果表明,所制备的混合烷基苯磺酸盐与胜利油田Ⅰ、Ⅱ类油藏4个区块原油的界面张力达到了5×10^-3mN/m以下,对Ⅲ类油藏原油界面张力达到3×10^-2mN/m,且具有较宽的浓度窗口、较高的耐盐性能、较低的吸附性能、与聚合物较好的配伍性能,综合性能明显优于同类产品。红外光谱、质谱和碳数分布分析结果表明其组成比石油磺酸盐复杂,更接近于原油的组成。     

探讨两种国产石油磺酸盐间产生协同效应的机理

克拉玛依石油磺酸盐与安庆石油磺酸盐是有代表性的两种国产石油磺酸盐，前者由新疆原油磺化中和制得，后者是以催化裂化馏分油为原料经磺化中和制得。笔者应用^1H NMR和元素分析的方法测定了这两种石油磺酸盐的脱磺油，从而得到石油磺酸盐亲油基的支化度和芳香度。应用相图和测定Krafft温度的方法考察了该两种国产石油磺酸盐的亲水亲油性，由此探讨了该两种石油磺酸盐间发生协同效应的基础。应用绘制界面张力等值图的方法优化了该两种石油磺酸盐的复配，筛选了针对不同试验区块油、水及温度条件的表面活性剂驱油配方，验证了该两种石油磺酸盐之间的正协同效应。     

系列化石油磺酸盐与胜利原油相互作用的研究

研究了胜利石油磺酸盐及其系列化产品与胜利原油及其组分之间的界面张力，结果表明，原油组成的差别造成磺化产品性质的差别；同一石油磺酸盐产品不能适应不同区块原油低张力的要求，必须复配适宜的助表面活性剂，而系列化石油磺酸盐与本区块油水具有较好的相似相容性，低浓度下不复配任何助表面活性剂就具有较高的界面活性。     

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).     

石油磺酸盐的结构与界面活性的关系及其质量评价

研究了石油磺酸盐的结构与界面活性之间的相互关系并对其进行了质量评价。实验结果表明,当石油磺酸盐溶液与原油的界面张力小于0.050 mN/m、介于0.05～0.150 mN/m或大于0.150 mN/m时,石油磺酸盐的界面活性分别表现为优异、良好和较差;质谱分析结果显示,石油磺酸盐试样中含有烷基苯、烷基萘、烷基茚满、烷基菲、烷基苊、烷基芴和烷基联苯磺酸盐7种类型的磺酸盐,当烷基苯、烷基萘、烷基茚满和烷基苊磺酸盐的质量分数分别为20.0%,5.2%,6.1%,4.6%左右时,试样具有一定的界面活性;待测试样与标准试样(试样9)的相关系数大于0.930时,该试样具有一定的界面活性,相关系数越接近1.000,界面活性越优异。     

三元复合驱用天然石油磺酸盐的制备及性能研究

研究了以大庆馏分油为原料 ,以发烟硫酸为磺化剂制备天然石油磺酸盐 ( NPS)的工艺。通过在特定的表面活性剂碱聚合物三元复合体系中大庆原油与驱替液的油水界面张力 ,从 6种馏分油中筛选出了适合三元复合驱用表面活性剂 NPS的亲油基原料。并研究了三元复合体系中 NPS的浓度、混合碱的浓度对界面张力的影响。用 IR确定了 NPS的结构 ,用柱层析法分析了 NPS产品组成。     

1-Phenylalkane Sulfonates for Studying Interfacial Tensions

Abstract

A series of 1-phenylalkane sulfonates with high purity were synthesized through a simple and effective way. Interfacial tension (IFT) of 1-phenylalkane sulfonates against crude oil from Daqing oil field in China was investigated, interfacial tension minima were observed with changes of surfactant concentrations and time. Alkali concentrations where lowest interfacial tensions were achieved moved to low regions by increasing the chain length of 1-phenylalkane sulfonates, namely, 1-phenyldodecane sulfonate at about 2.2%, 1-phenyltetradecane sulfonate at about 0.6%, 1-phenylhexadecane sulfonate at about 0.3%. No minima were observed when interfacial tensions of pure 1-phenylalkane sulfonates against alkanes were measured. The phenomenon is quite distinct from that of 1-phenylalkane sulfontes against crude oil.     

HYDROLIQUEFACTION OF TEXAS LIGNITE IN COAL- AND PETROLEUM-DERIVED SLURRY OILS

ABSTRACT

Hydroliquefaction of Texas lignite (68.5%. C daf) was conducted in a batch autoclave under hydrogen in a coal–derived slurry oil at 90 bar initial pressure for temperatures of 380–460^° C and residence time of 15–60 minutes, or a vacuum distillate from petroleum at 435^° C for 60 minutes and initial H₂–pressure of 60–150 bar, or a vacuum residue from the same petroleum at 435 and 460^° C for 60 minutes and initial H₂–pressure of 90–150 bar or tetralin at 435^°C, 60 minutes and 90 bar initial H₂–pressure. Red mud plus sodium sulfide were added as a catalyst for all experiments. Lignite conversion ranged from 50 to 83%. The products were separated into gases, residue, asphaltenes, oils B,P. above 200^° C, oils B.P. below 200^° C. Total liquid products from coal reached 57% in coal-derived slurry-oil, 56% in vacuum distillate and 64% in vacuum residue at optimum conditions with 32% of product oil B.P. below 200^° C in vacuum distillate and 24% in vacuum residue. When coprocessing lignite with vacuum residue at 120 bar initial pressure, 435^°C and 60 minutes residence time the total mass balance presented an oil yield of 73%. with 32% boiling below 200^°C.     

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.     

石油磺酸盐中极性组分的协同效应

采用硅胶柱层析法将两种石油磺酸盐分别分离成不同极性组分,在加醇和无醇条件下考察了石油磺酸盐不同极性组分及其复配体系的相行为和超低界面张力。将不同极性组分按一定比例复配,在加醇条件下可形成中相微乳液,且可获得较高的增溶参数和超低界面张力。在无醇条件下,石油磺酸盐单独组分均不能形成中相微乳液,合理复配两种或三种不同极性组分,不但可以形成中相微乳液且可获得较高的增溶参数和超低界面张力,相行为参数随复配比例的变化而变化。在上述实验的基础上提出石油磺酸盐是由不同极性组分组成的复杂表面活性剂,其不同极性组分间存在协同效应,极性在协同效应中起着重要作用。建议根据不同极性组成比例来监控石油磺酸盐产品质量。     

Preparation and Characterization of Petroleum Sulfonate Directly from Crude

Abstract

Sulfonate surfactants used in enhanced oil recovery (EOR) need not be very pure, such as linear alkyl benzene sulfonate, but should be similar in terms of surface activity. The possibility of preparation, isolation, and purification of petroleum sulfonate directly from crude is studied in the lab. Crudes chosen in this study are GSPC and Panna supplied by Oil and Natural Gas Corporation (ONGC), India. Crude is digested with sulfuric acid (98%) or oleum (20%) for sulfonation and then neutralized with sodium hydroxide. Finally, sulfonate surfactant is isolated and purified by a series of solvent extraction procedures using alcohols and alkanes. The sulfonate surfactant obtained is characterized with respect to EOR applicability, e.g., surface tension measurement and interfacial tension measurement against benzene. The dosing of the sulfonating agent was verified to study its effect on yield of sulfonate and surface tension value. The yield of sulfonate increases with the increase in dosing of the sulfonating agent; however, the surface activity of sulfonate decreases. Optimum yield and surface activity are obtained for sulfonate surfactants produced from GSPC crude when a crude-to-sulfonating agent volume ratio of 1:5 is used. Surface activity of sulfonate surfactant obtained from GSPC crude compares well with commercially available surfactant, TRS 10-80, used in EOR. This study also brings the possibility of an in situ generation of sulfonates in oil fields for EOR.     

孤岛油田调驱试验中高效驱油剂的研究

用绘制界面张力等值图的方法,对两种石油磺酸盐复配结果进行了优化,筛选出可与孤岛油田原油产生最低平衡油水界面张力的石油磺酸盐配方(0.25%KPS+0.22%APS),并通过室内驱油试验验证了配方的驱油能力。结果表明,将不同来源的性质和结构互补的两种石油磺酸盐进行复配,可与原油产生超低界面张力(3.4×10~(-4)mN/m)。同时证实聚合物的存在不影响油水界面张力平衡值,只延缓油水界面张力达到平衡的时间。注入0.3倍孔隙体积的高效驱油剂,能提高原油采收率17%;在聚合物驱后注入时间越早,最终原油采收率就越高。     

表面活性剂增效碱驱中表面活性剂之间的协同效应

本文考虑了在碱（Ｎａ２ＣＯ３）性条件下表面活性剂之间在界面张力性质、耐盐性及驱油效率等方面的协同效应。实验结果表明，阴离子表面活性剂（石油磺酸盐）与非离子表面活性剂之间的复配，除在界面张力性质方面显现出比石油磺酸盐之间更好的协同效应外，石油磺酸盐在较高矿化度下的溶解性也获得根本改善，能够顺利通过孔隙介质并获得较高的驱油效率，长期放置亦无沉淀发生，为热力学稳定体系。     

石油羧酸盐和磺酸盐复配体系的界面活性

研究了用石油馏分液相氧化产物制得的石油羧酸盐与不同磺酸盐（ＯＲＳ－４１、Ｂ－１００、ＭＳ－４５等）的复配体系的界面活性。结果表明,复配体系的界面生优于单一的石油羧酸或磺酸盐体系。复配体系的这些特点对提高驱油效率很有利。     

1-Phenylalkane Sulfonates for Studying Interfacial Tensions

A series of 1-phenylalkane sulfonates with high purity were synthesized through a simple and effective way. Interfacial tension (IFT) of 1-phenylalkane sulfonates against crude oil from Daqing oil field in China was investigated, interfacial tension minima were observed with changes of surfactant concentrations and time. Alkali concentrations where lowest interfacial tensions were achieved moved to low regions by increasing the chain length of 1-phenylalkane sulfonates, namely, 1-phenyldodecane sulfonate at about 2.2%, 1-phenyltetradecane sulfonate at about 0.6%, 1-phenylhexadecane sulfonate at about 0.3%. No minima were observed when interfacial tensions of pure 1-phenylalkane sulfonates against alkanes were measured. The phenomenon is quite distinct from that of 1-phenylalkane sulfontes against crude oil.     

用气相色谱-质谱法分析三次采油用石油磺酸盐的结构

采用萃取法纯化工业石油磺酸盐试样;在N,N-二甲基甲酰胺溶液中以三氟乙酸酐为Lewis酸、KI为强亲核试剂,对纯化后的石油磺酸盐进行快速还原衍生化,并对衍生产物进行GC-MS分析。实验结果表明,当衍生反应体系中的n(石油磺酸盐)∶n(KI)∶n(三氟乙酸酐)=1∶20∶20时,衍生效果最优。采用HP-5石英毛细管柱,在程序升温(起始温度90℃保持2min,然后以4℃/min的速率升至300℃,保持10min)的GC分析条件下,石油磺酸盐衍生产物及其同分异构体得到有效分离。MS分析结果表明,石油磺酸盐试样中含有4种异构的癸烷基苯磺酸盐、4种异构的十一烷基苯磺酸盐、5种异构的十二烷基苯磺酸盐和6种异构的十三烷基苯磺酸盐。     

石油羧酸盐与不同碳链结构磺酸盐复配体系的界面活性研究

为了探求石油磺酸盐与石油羧酸盐复配后产生协同效应的机理,选出直链和支链的石油磺酸盐与石油羟酸盐复配,并测定复配体系的界面张力,研究复配后的界面活性。发现直链的石油磺酸盐复体系要优于支链的碘酸盐复配体系的界面活性,由此讨论了复配效果和石油磺酸盐,石油羧酸盐分子结构及亲水亲油差异的关系。结果表明,直链磺酸盐与石油羧酸盐复配表面出很好的复配效应,而支链磺酸盐与石油羧酸盐复配效果较差。     

有机碱三元复合驱油体系与胜利原油的协同作用

采用旋转滴法测定了胜利石油磺酸盐与不同区块原油的油水界面张力,考察了有机碱乙醇胺及聚合物对体系界面张力的影响,测定了复合驱体系的粘度。实验结果表明,乙醇胺和胜利石油磺酸盐之间存在降低油水界面张力的协同效应,在适宜的乙醇胺浓度条件下,界面上的石油酸、反应生成的石油酸皂和石油磺酸盐混合吸附,界面张力达到最低。聚合物对界面张力总体影响不大。有机碱三元复合驱体系的粘度变化不大。     

减压渣油中钙赋存状态的研究

利用酸解的方法将低凝稠油减压渣油和超稠油减压渣油中的石油酸钙变为有机酸,采用醇碱溶液抽提的方法将石油酸抽提出来,通过红外光谱表征,证明是支化度较高、侧链较短的环烷酸。根据抽提物的模拟蒸馏数据对2种原油脱钙后柴油馏分和润滑油馏分酸值的增加情况进行了估算。     

二元无碱驱油体系的室内研究与评价

随着三元复合驱技术研究的不断深入, 三元复合驱体系中碱对石油开采过程及地层造成的危害日益凸现。以自制石油磺酸盐NPS-2为表面活性剂, 通过考察不同质量分数的NaCl和石油磺酸盐对大庆采油四厂油水界面张力的影响, 确定了二元无碱驱油体系配方, 并对该体系的应用广泛性和驱油效果进行了评价。结果表明, 从自制石油磺酸盐为表面活性剂, 二元无碱驱油体系合适配方为C_NaCl=0.6%~1.2%, C_NPS-2=0.1%~0.3%, C_HPAM=0.12%. 该二元复合驱配方体系可使油水界面张力降至超低, 全部达到10^-3mN/m 数量级, 最低可达10^-4mN/m 数量级, 能够避免由碱引起的对地层和采油设备的损害, 具有很高的现场应用价值。