高盐油藏下两性/阴离子表面活性剂协同获得油水超低界面张力

研究了在高盐油藏中, 利用两性/阴离子表面活性剂的协同效应获得油水超低界面张力的方法. 两性表面活性剂十六烷基磺基甜菜碱与高盐矿化水具有很好的相容性, 但在表面活性剂浓度为0.07%-0.39%(质量分数)范围内仅能使油水界面张力达到10^-2 mN·m^-1量级, 加入阴离子表面活性剂十二烷基硫酸钠后则可与原油达到超低界面张力. 通过探讨表面活性剂总浓度、金属离子浓度、复配比例对油水动态界面张力的影响, 发现两性/阴离子表面活性剂混合体系可以在高矿化度、低浓度和0.04%-0.37%的宽浓度范围下获得10^-5 mN·m^-1量级的超低界面张力, 并分析了两性/阴离子表面活性剂间协同获得超低界面张力的机制.     

阴阳离子表面活性剂体系超低油水界面张力的应用

通过阴阳离子表面活性剂复配,在实际油水体系中获得了超低界面张力.通过在阴离子表面活性剂分子结构中加入乙氧基(EO)链段,以及采用阴阳离子加非离子型表面活性剂的三组分策略,有效解决了混合表面活性剂在水溶液中溶解度问题.进而研究了阳离子表面活性剂结构、非离子表面活性剂结构、三者组分配比、表面活性剂总浓度等因素对油水界面张力的影响,从而在胜利油田多个实际油水体系中获得了较大比例范围和较低浓度区域的油水超低界面张力,部分体系甚至达到了10-4 mN·m-1.由于阴阳离子表面活性剂间强烈的静电吸引作用,相关体系具有很好的抗吸附能力.经过石英砂48 h吸附后,体系仍然具有很好的超低界面张力.     

OCS表面活性剂在弱碱、无碱条件下的界面张力性能研究

研究了OCS表面活性剂中试产品在弱碱NaCO33及无碱条件下应用于不同油田原油的油-水界面张力特性。结果表明：对于大庆采油四厂原油，当表活剂浓度为0．1％-0．3％，Na2CO3浓度为0．6％-1．2％时，油-水界面张力可达到超低(-l0^-3mN／m数量级)；对于大庆采油二厂原油，当表面活性剂浓度为0．1％-0．3％，Na2CO3浓度为0．8％-1．4％时，油-水界面张力可达到超低；对于华北油田古-联原油，当表面活性剂浓度为0．2％，NaCO3浓度为0．6％-1．2％时，油-水界面张力可达到超低；对于胜利油田孤东采油厂原油，当表面活性剂浓度为0．2％，NaCO3浓度为0．8％-1．4％时，油-水界面张力可达到超低。在无碱条件下，对于大港油田枣园1256断块原油，当OCS表面活性剂浓度达到0．1％时，油-水界面张力即可达到超低；对于江苏油田原油，当OCS表面活性剂浓度在0．1％以上时，油-水界面张力均可以达到10^-2mN／m数量级。聚丙烯酰胺聚合物的加入对油-水超低界面张力的形成和稳定具有促进作用。     

壬基酚甜菜碱两性表面活性剂的合成和抗温耐盐性能

以壬基酚、环氧氯丙烷、二甲胺和3-氯-2-羟基丙磺酸钠为原料, 在催化剂的作用下经醚化、叔胺化、季铵化, 合成了壬基酚甜菜碱两性表面活性剂(NSZ), 并确定了最佳的反应条件。 壬基酚氯醇醚的最佳合成条件:物料比n(壬基酚):n(环氧氯丙烷)=1:4, 催化剂四丁基溴化铵用量为壬基酚用量的4%(摩尔比), 反应时间为4 h, 反应温度为95 ℃。 壬基酚叔胺的最佳合成条件:物料比为n(壬基酚氯醇醚):n(二甲胺):n(氢氧化钠)=1:2.5:1.1, 反应时间为4 h, 反应温度为60 ℃。 NSZ的最佳合成条件:以异丙醇/水为溶剂且其体积比为2:1, 反应温度为85 ℃, 反应时间24 h, n(3-氯-2羟基丙磺酸钠):n(壬基酚叔胺)=1.2:1, 反应体系的pH值为8~9。 通过测定NSZ在高温高矿化度条件下的界面性能、乳化性能和热稳定性, 证明了NSZ具有良好的耐温抗盐性能。     

CMC系列高分子表面活性剂与原油 超低界面张力形成机理的研究

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素系列高分子表面活性剂与大庆原油形成超低界面张力的机理.结果表明,CMC系列高分子表面活性剂具有与低分子量表面活性剂相比拟的表/界面活性,其水溶液的表面张力可达28～35mN/m,界面张力达到10     

CMC系列高分子表面活性剂与原油超低界面张力形成机理的研究

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素系列高分子表面活性剂与大庆原油形成超低界面张力的机理.结果表明,CMC系列高分子表面活性剂具有与低分子量表面活性剂相比拟的表/界面活性,其水溶液的表面张力可达2835mN/m,界面张力达到10^-110mN/m.碱的加入可显著降低高分子表面活性剂与原油的界面张力,在适当条件下界面张力达到超低值(10^-3mN/m),可望作为三次采油的驱油剂.等效烷烃模型研究表明,用碱与原油酸性组分的作用来解释碱能使界面张力下降至超低值的传统观点是不完善的,加入碱能使高分子表面活性剂胶束解缔,胶束数量增多,胶束粒径减小,单分子自由链增加,有利于高分子表面活性剂向界面迁移和排布,这是高分子表面活性剂和碱复配体系与原油界面张力下降至超低值的主要原因.     

两性表面活性剂插层GO-LDH的制备和性能

以层状氧化石墨烯-锌铝类水滑石(GO-LDH)为主体,两性表面活性剂(ZS)(十二烷基羧基甜菜碱(DCB)、十二烷基磺基甜菜碱(DSB)和N-十二烷基-β-氨基丙酸钠(DAP))为客体,制备ZS/GO-LDH杂化物。采用粉末X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重/差热分析(TGA/DTA)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等手段对其进行表征,考察制备方法、表面活性剂用量、溶剂和反应时间等对杂化物结构的影响。结果表明,采用离子交换法成功将DCB和DSB插层GO-LDH。以水为溶剂合成的DCB/GO-LDH和DSB/GO-LDH层间距分别为2.87～3.29、3.48 nm,比N-甲基吡咯烷酮(NMP)为溶剂制备的杂化物(1.25和1.31 nm)更大。另外,DCB/GO-LDH和DSB/GO-LDH的热分解行为与对应的DCB/GO和DSB/GO类似,但前者中DSB的燃烧温度比后者高45℃,这可能与其和层板相互作用强度有关。此外,研究了CPF-DCB/GO-LDH在pH=5.0和6.8的缓冲液中毒死蜱(CPF)的释放行为。结果表明CPF-DCB/GO-LDH具有一定的缓释性能,释放行为可以用准二级动力学和抛物线扩散模型来描述。     

十二烷基硫酸钠对两性咪唑类离子液体表面活性剂1-磺丙基-3-十二烷基咪唑内盐界面聚集行为的影响

利用界面扩张流变技术,研究了两性咪唑类离子液体表面活性剂1-磺丙基-3-十二烷基咪唑内盐(C₁₂imSP)的界面聚集行为,探讨传统表面活性剂十二烷基硫酸钠(SDS)对C₁₂imSP界面聚集行为的影响机制。 结果表明,少量SDS的加入可以填补界面上疏松的C₁₂imSP分子间的空位,界面上形成表面活性剂混合吸附膜,界面张力显著降低;提高SDS的浓度,其分子从体相向界面层的扩散交换占优势,界面层分子逐渐达到饱和吸附,此后体系中有混合胶束形成。 体相胶束中富集的SDS分子对C₁₂imSP分子的“收纳”作用及进一步的“挽留”作用,加之C₁₂imSP分子本身相对较大的空间位阻效应导致界面上的C₁₂imSP分子一旦通过扩散作用被交换至体相,其很难再回复到表面层,即界面膜以SDS分子为主。 通过调节体系中SDS的含量,可以实现对混合体系SDS/C₁₂imSP/NaCl(0.1 mol/L)界面聚集行为的调控,进而实现对界面膜性质的调控。     

阴离子表面活性剂在油水界面聚集的分子动力学模拟

用分子动力学方法模拟了油、水和阴离子表面活性剂组成的混合溶液从初始“均相”到“油水两相”分离的动力学过程, 研究了十二烷基苯磺酸钠(SDBS)在界面分离过程中的作用. 模拟发现, 油水两相能够在短时间内分离达到平衡, 形成一个明显的油水界面; 在SDBS存在情况下, 油水界面的分离时间随着SDBS浓度的增加逐渐增加, 达到平衡时SDBS会在界面处形成一个明显的界面膜, 并对油水界面处的水分子有限制作用. 模拟表明, 分子动力学方法可以作为实验的一种补充, 为实验提供必要的微观分子结构信息.     

羟基磺基甜菜碱氟碳表面活性剂在油水界面的扩张粘弹性

氟碳表面活性剂是目前表面活性最高的特种表面活性剂,在三次采油等领域具有良好的应用前景。 用小幅周期振荡法研究了羟基磺基甜菜碱型氟碳表面活性剂(FS)在油-水界面的扩张粘弹性能,考察了振荡频率、FS质量分数、无机盐(NaCl、CaCl₂、MgCl₂)对FS在油-水界面的扩张粘弹性能的影响。 结果表明,FS溶液在油水界面的扩张模量、扩张弹性和扩张粘度随着FS质量分数的增加而出现最大值,随着频率的增大而略有增加。 加入无机盐时,扩张模量、扩张弹性随NaCl质量分数增大而出现最大值,而随着CaCl₂或者MgCl₂质量分数的增加,FS溶液的扩张模量、扩张弹性和扩张粘度减小,而当CaCl₂或者MgCl₂质量分数分别为0.05%、0.1%时,tanθ达到最大值。     

Ultra-Low Interfacial Tension Between Heavy Oil and Betaine-Type Amphoteric Surfactants

Betaine surfactants with lipophilic groups of different lengths were synthesized in this research and the dynamic interfacial tension (IFT) between solutions of these surfactants and three kinds of crude oil from Shengli Oilfield are measured. The results indicated that, for Gudao and Gudong heavy oil, cetyl dimethyl hydroxyl sulfobetaine (SBET-16) was the most efficient in lowering the IFT in the case of no alkalis, while for Shengtuo heavy oil, cetyl dimethyl carboxymethyl betaine (CBET-16) was best. SBET-16 with the concentration of 0.003–0.1% and 0.005–0.1% can reduce the oil/water IFT to ultra-low for Gudao and Gudong oil respectively, CBET-16 with the concentration of 0.005–0.1% can lower the oil/water IFT to ultra-low for Shengtuo oil. These results showed that for different oils, an oil displacement agent with high capacity to lower the oil/water interfacial tension may be obtained only by changing the molecular structure of betaine surfactant. This study can be used to guide the design of surfactants for alkaline-free combination flooding.     

Studies of Interfacial Activities of Four Kinds of Surfactants at Oil/Water Interface

This article aims to compare the interfacial activities of different kinds of surfactants in the same oil/water system. The anionic surfactants of alkylbenzene sulfonates, the polyoxyethylenated nonionic surfactants, the cationic surfactants of alkyl trimethyl ammonium chlorides, and the zwitterionic surfactants of alkyl hydroxyl sulfobetaines were used, and the interfacial tensions of the surfactant solutions against kerosene at different NaCl concentrations were measured. It is found that the interfacial activities of the alkylbenzene sulfonates are high and ultralow interfacial tensions (<0.01 mN/m) can be obtained at proper salinities. While, the nonionic surfactants have relatively low interfacial activities and the minimum tensions are around 0.01 mN/ms. The salinity scanning curves of the alkylbenzene sulfonates and nonionic surfactants decrease first, then increase, showing their interfacial activities can be changed by the salinity effectively. The cationic and zwitterionic surfactants have very low interfacial activities, of which all the tensions are higher than 0.1 mN/ms and are hard to be changed by the salinity. The experimental results may have important reference values for enhanced oil recovery.     

Effect of Crude Oil Fractions on Interfacial Tensions of Novel Sulfobetaine Solutions

The dynamic interfacial tensions (IFTs) of two novel zwitterionic surfactants with different hydrophobic groups, alkyl sulfobetaine (ASB), and xylyl substituted alkyl sulfobetaine (XSB), against kerosene, crude oil, and model oils containing crude oil fractions, such as resins, asphaltenes, saturates, aromatics, and acidic fractions, have been investigated by a spinning drop interfacial tensiometer. The experimental results show that XSB solutions show higher interfacial activity than ASB against kerosene because of the larger size of the hydrophobic part of the XSB molecule. The petroleum acids have high interfacial activity and can adsorb onto the interface. For ASB solutions, the synergism mixed adsorption of betaine and acid molecules lowers IFT values. On the one hand, the partly displacement of XSB molecules by petroleum acid at the interface results in the increase of IFTs. Therefore, resins, aromatics, and acidic fractions show strong effects on IFTs of betaine solutions. On the other hand, asphaltenes and saturates have little effect on interfacial properties. Moreover, the hydrophilic part of the betaine molecule at the interface may vary its orientation from vertical to flat with aging time. Therefore, the dynamic IFT curves of ASB solutions against model oils show “V” shape for resins, aromatics, and acidic fractions.     

废动植物油脂制备烷醇酰胺的研究

以废动植物油脂为原料,在自制DYD催化剂作用下制得脂肪酸甲酯,再以氢氧化钾为催化剂,与二乙醇胺合成烷醇酰胺。考察了反应温度、反应时间、催化剂用量、真空度等因素对反应的影响,通过单因素实验和析因实验确定最佳工艺条件为:甲酯/二乙醇胺物质的量比1∶1.55,反应温度110℃,反应时间2.5 h,真空度0.08 MPa,催化剂用量0.65%(相对于脂肪酸甲酯的质量),烷醇酰胺的收率达96.3%。通过红外光谱对产物结构进行了表征,并对界面张力进行了测定。结果表明,产物具有较好的界面活性。     

基于强化界面润湿调控的多羟基苯磺酸盐驱油剂的合成与性能评价

通过调控原油-岩石界面润湿性进而提高采收率是油田高效开发的重要思路.现有阴离子表面活性剂改变岩石表面润湿性能力有限,研发强化界面润湿调控性能的新型驱油剂具有重要应用意义.本工作合成了一种新型表面活性剂二羟甲基十二烷基苯磺酸钠(SDDBS),通过红外和核磁进行结构表征,探究了SDDBS在亲油岩石表面的吸附行为、降低油水界...     

Biodiesel Production by Single and Mixed Immobilized Lipases Using Waste Cooking Oil

Biodiesel is one of the important biofuels as an alternative to petroleum-based diesel fuels. In the current study, enzymatic transesterification reaction was carried out for the production of biodiesel from waste cooking oil (WCO) and experimental conditions were optimized, in order to reach maximum biodiesel yield. Bacillus stearothermophilus and Staphylococcus aureus lipase enzymes were individually immobilized on CaCO₃ to be used as environmentally friendly catalysts for biodiesel production. The immobilized lipases exhibited better stability than free ones and were almost fully active after 60 days of storage at 4 °C. A significant biodiesel yield of 97.66 ± 0.57% was achieved without any pre-treatment and at 1:6 oil/methanol molar ratio, 1% of the enzyme mixture (a 1:1 ratio mixture of both lipase), 1% water content, after 24 h at 55 °C reaction temperature. The biocatalysts retained 93% of their initial activities after six cycles. The fuel and chemical properties such as the cloud point, viscosity at 40 °C and density at 15 °C of the produced biodiesel complied with international specifications (EN 14214) and, therefore, were comparable to those of other diesels/biodiesels. Interestingly, the resulting biodiesel revealed a linolenic methyl ester content of 0.55 ± 0.02% and an ester content of 97.7 ± 0.21% which is in good agreement with EN14214 requirements. Overall, using mixed CaCO₃-immobilized lipases to obtain an environmentally friendly biodiesel from WCO is a promising and effective alternative for biodiesel production catalysis.     

阴阳离子表面活性剂混合体系在克拉玛依油田中获得超低界面张力

利用阴阳离子表面活性剂复配技术,在克拉玛依油田实际油水体系中获得了超低界面张力.通过添加非离子保护剂的第三组分,阴阳离子表面活性剂混合体系在克拉玛依油田回注水体系中的溶解度大大提高.确定了相关体系能够获得超低界面张力的表面活性剂的浓度和混合的比例范围,在克拉玛依油田的多个实际油水体系中获得了具有较大复配比例和较低表面活性剂浓度的实际配方,其中部分体系油水界面张力可接近10-4mN·m-1.同时,这类阴阳离子表面活性剂混合体系具有很好的抗吸附能力,在石英砂吸附72 h后体系依然呈现优良的超低界面张力.     

Dissipative Particle Dynamics Study of Interfacial Properties and the Effects of Nonionic Surfactants on Hydrocarbon/Water Microemulsions

The aim of this work was to apply dissipative particle dynamics (DPD) mesoscopic simulations to study the interfacial orientation and the effect of the nonionic surfactant, hexaethylene glycol monododecyl ether (C₁₂E₆), on different (oil (dodecane)/water) microemulsion systems. The Hildebrand-solubility-parameter model and Flory–Huggins/Hansen-solubility-parameter (FH/HSP) model were combined to evaluate the DPD interaction parameter (a_ij) where the solubility parameters (δ_i) as DPD input parameters were preliminary validated by all-atom molecular dynamics (MD) results and experimental data. The interfacial property dependence of dodecane/water/C₁₂E₆ system on the oil/water (o/w) ratio and on the concentration of surfactant and orientation at the interface were investigated. It was found that the surfactant addition reduced the IFT of o/w interfaces and this reduction was more efficient for water-in-oil microemulsions (o/w ≤ 1).     

Waste Cooking Oil-Modified Epoxy Asphalt Rubber Binders with Improved Compatibility and Extended Allowable Construction Time

The application of crumb rubber from end-of-life tires and waste cooking oil (WCO) in road pavements is of significant importance from an economic and environmental viewpoint. However, the incorporation of crumb rubber greatly shortens the allowable construction time of epoxy asphalt binders due to the high viscosity of the epoxy asphalt rubber (EAR) binder and poor compatibility between crumb rubber and asphalt binder. To lower the viscosity of asphalt rubber, extend the allowable construction time and improve the compatibility of EAR binder, waste cooking oil (WCO) was introduced. The effect of WCO on the viscosity–time behavior, thermal stability, dynamic modulus, glass transitions, crosslink density, damping ability, compatibility, mechanical properties and phase separation of WCO-modified EAR binders was investigated by using the Brookfield viscometer, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine and laser confocal microscopy. The test results demonstrated that the incorporation of WCO declined the viscosity and extended the allowable construction time of the unmodified EAR binder. The inclusion of WCO improved the compatibility between asphalt and crumb rubber and the damping ability and elongation at the break of the unmodified EAR binder. The presence of WCO had a marginal effect on the thermal stability of the unmodified EAR binder. Confocal microscopy observation revealed that asphalt rubber particles aggregated in the epoxy phase of the unmodified EAR binder. With the inclusion of WCO, co-continuous asphalt rubber particles became more spherical.