长庆油田石油磺酸盐中活性组分识别

石油磺酸盐中活性组分的识别对于磺化原料油的选择和磺酸盐产品界面活性的稳定具有重要的指导意义.开展石油磺酸盐关键活性物质结构的确定与活性检测研究,可以提升高品质石油磺酸盐生产的可控性.采用液相色谱制备技术,结合质谱分析和界面张力测试评价,从长庆石油磺酸盐样品中成功分离制备出了具有优异界面活性的关键活性组分.试验结果表明,其活性组分占总石油磺酸盐含量的7.3%,可以将油水界面张力快速降至超低(<1.0×10^(-3) mN/m),且具有广泛的油相普适性,对于正己烷~正十六烷油相以及多种油田来源原油,均可将油水界面张力降至超低.此外,活性组分以单磺酸盐为主,平均相对分子质量为414(不含Na^(+)),相对分子质量分布范围在380~450之间,主要组成是以多种同分异构体结构形式存在的十七烷基苯磺酸盐和十八烷基苯磺酸盐混合物.     

电喷雾质谱法对重烷基苯的族组成分析与结构鉴定

建立了一种系统的分析重烷基苯的方法。通过柱色谱对重烷基苯进行了分离，将其分成了六个族组分，对这六个族组分进行红外、紫外以及荧光鉴定，确定了各族组分的归属，利用电喷雾质谱测定了第二到第五族组分磺酸盐的相对分子量分布，结合红外、紫外所测定的结果，及每族物质的不饱和度和通式，推算出了烷基芳烃部分的相对分子质量和烷基苯的碳数分布。     

电喷雾质谱法分析三次采油用石油磺酸盐

采用电喷雾质谱法测定了胜利油田三次采油用石油磺酸盐样品的分子量分布范围在200～600,数均分子量为488,重均分子量为534.鉴别出烷基苯磺酸盐、烷基萘磺酸盐、烷基茚满磺酸盐等为胜利油田磺酸盐的主要组分.同时对来自胜利、大庆、克拉玛依和玉门4个不同油田的石油磺酸盐进行区别分析.     

气相色谱-质谱法解析重烷基苯异构体的烃基结构

<正>重烷基苯(HAB)是生产十二烷基苯过程中的副产物,产量约占烷基苯的10%,主要用于生产采油驱油剂、润滑油添加剂和导热油等~([1-2])。以重烷基苯为原料合成的重烷基苯磺酸盐具有优良的降低油/水界面张力的特性,将其作为驱油剂用于三次采油中,可大幅度提高采油率,成为三次采油中最重要的驱油用表面活性剂~([3]),其驱油机理还有待于进一步深入研究,有研究表明烃基结构是影响其使用性能的重要因素之一~([4-5])。重烷基苯是一种复杂的混合物,其组成极不稳     

ASP复合驱油体系瞬时界面张力的研究

以胜利油田孤岛试验区原油为油相,用正交试验筛选了碱/天然混合羧酸盐/聚合物驱油体系,讨论了各组分对ASP复合驱油体系油水瞬时界面张力的影响,并探讨了各组分间的相互作用机理及其在油水界面的吸附机理。     

羟基取代的烷基苯磺酸盐在水/气和水/癸烷界面的结构特点（摘要）

驱油表面活性剂的分子设计是一项重要的研究课题.设计新型高效的驱油表面活性剂关键的问题在于如何洞察表面活性剂的结构和功能的关系.长线性烷基苯磺酸盐是一类非常流行的表面活性剂,广泛应用于工业和日常生活中.关于烷基苯磺酸盐的结构和功能研究已有大量的实验和理论工作报道.近来,结合分子设计的思想,实验上合成了新型的羟基取代的烷基苯磺酸盐表面活性剂,并研究了这类新型表面活性剂动态的界面行为.我们从理论上利用分子动力学模拟的方法研究了羟基取代的烷基苯磺酸盐单分子层在水/气和水/癸烷界面的结构特点.从液体密度剖面图、氢键、表面活性剂聚集结构和有序参数等方面,详细报道了2-羟基-3-癸基-5-辛基苯磺酸钠这种新型阴离子表面活性剂的界面特征.模拟结果表明随着表面活性剂分子数目的增加,每个表面活性剂在单分子层上形成分子内氢键的平均数目将下降,但形成分子内氢键的结构仍处于主导地位;烷基尾链的疏水部分,尤其是苯环3号位上取代的癸基随着表面活性剂覆盖度增大,向界面外延伸并且更加有序;二维径向分布函数描绘了表面活性剂聚集结构的特点并暗示了癸烷相将影响表面活性剂疏水部分的取向;表面活性剂分子容易形成长程氢键结构.我们的模拟结果是对实验研究的一个重要补充.此外,模拟中我们利用gromacs和ffamber程序,使用了全原子模型,这将为模拟烷基苯磺酸盐表面活性剂的界面行为提供新的方案.     

DSB显著提高羧酸盐驱油体系抗钙镁离子能力的研究

测定了工业品级的天然混合长链烷基羧酸盐(SDC)以及与3-(N,N-二甲基十二烷基胺)-2-羟基-丙磺酸(DSB)复配驱油体系的界面张力(ITFmin), 分别得出其抗钙镁离子的能力为400和5000 mg/L. 选择试剂级十二烷基羧酸钠与DSB复配, 测定了不同配比溶液的表面张力值和临界胶束浓度cmc, 结合长链烷基脂肪酸与钙离子的溶度积Ksp, 分析了对不溶性长链烷基羧酸盐形成的影响. 根据现场驱油体系配方, 计算了两者在溶液中的摩尔配比为4:1时的十二烷基羧酸盐在胶束中的摩尔分数xm1为0.51, 相互作用参数βm值为-3.11, 反映了两者有较强的相互作用. 采用量子化学方法, 对由1个十二烷基羧酸分子、1个DSB分子及1个二价钙离子组成的模型复合物进行了能量计算和电荷分布计算, 得出在长链烷基羧酸盐和DSB两者混合胶束的界面层中存在负电荷空穴, 提出二价金属离子被络合的模型, 合理地解释了实验事实.     

驱油用磺酸盐表面活性剂的研究进展

综述了驱油用石油磺酸盐、重烷基苯磺酸盐、脂肪醇聚氧乙烯醚磺酸盐及磺酸盐双子表面活性剂四种磺酸盐表面活性剂的研究进展,指出了这四种表面活性剂在油田应用中存在的问题以及未来的发展方向;阐述了油水乳化提高原油采收率的机理,初步分析了影响表面活性剂乳化能力的因素,强调了从分子结构的角度研究表面活性剂性能的重要性.     

系列烷基苯磺酸盐对烷烃的动态界面张力研究

从表面活性剂分子量、表面活性剂浓度、电解质浓度、烷烃碳数等方面考察了系列烷基苯磺酸盐异构体纯化合物的油水动态界面张力行为.研究表明,表面活性剂分子量增大和电解质浓度增加使界面张力动态变化减慢,达到平衡所需时间延长;表面活性剂浓度增加和烷烃碳数增加使界面张力动态变化加快,达到平衡所需时间减少.     

“拟双子”阴离子表面活性剂在癸烷/水界面的分子动力学模拟

采用全原子分子动力学模拟方法研究了壬基酚取代的系列烷基磺酸盐表面活性剂在癸烷/水界面的微观聚集行为,通过分析界面厚度、界面生成能和界面张力以及表面活性剂分子与水分子之间的径向分布函数和配位数,讨论了不同磺烷基链长度对壬基酚基取代烷基磺酸盐表面活性剂界面性质的影响.结果表明,磺烷基链长为12时,表面活性剂的界面张力最低,界面厚度和界面生成能最大.     

脂肪醇聚氧乙烯醚磺酸钠的性能研究

对合成的不同碳链脂肪醇聚氧乙烯醚磺酸钠(AnESO,EO=3,n=14,16,18)的应用性能及与重烷基苯磺酸钠(HABS)的复配进行了研究.结果表明:(1)AnESO的γcmc分别为36.16 mN·m-1,35.47 mN·m-1和34.85 mN·m-1,A14ESO发泡性较好,A18ESO稳泡性较强,耐钙稳定性分别达到了8700mg/L,9500mg/L和10000mg/L,耐盐性为A18ESO ＞ A16ESO ＞A14ESO;(2)AnESO与HABS复配可以改善HABS的耐盐性,AnESO/HABS体系与大庆原油间的界面张力在ω(AnESO):ω(HABS)约为3:7时最低,达到了3.9×10-2mN·m-1,1.4×10-2mN·m-1和4.3×10-3mN·m-1,A18ESO/HABS体系油水界面张力在NaCl含量为0～15000mg·L-1下均达到10-3mN·m-1数量级.     

Adsorption,wetting, foaming,and emulsification properties of mixtures of nonylphenol dodecyl sulfonate based on linear alpha-olefin and heavy alkyl benzene sulfonate

Nonylphenol dodecyl sulfonate (C₁₂NPAS) has been synthesized, and mixed with heavy alkyl benzene sulfonates (HABS) in different proportions. The effects of different mixing ratios on properties such as adsorption, wetting, foaming, and emulsification, of the C₁₂NPAS/HABS surfactant mixtures have been systematically investigated. Experimental results have shown that, after mixing, the wetting and foaming properties of C₁₂NPAS/HABS are improved remarkably. Compared with C₁₂NPAS and HABS alone, the adsorption and emulsifying properties of C₁₂NPAS/HABS are far superior, which we attribute to a synergistic effect between these surfactants.     

大庆油田三元复合驱结垢样品中碳酸钙的结晶特性及形貌特征

采用EDAX, XRD和SEM等方法对大庆油田三元复合驱结垢样品中碳酸钙的结晶特性及形貌特征进行了研究. 结果表明, 结垢样品中的碳酸钙呈现出球形、棒状和花状等形貌特征和层状生长的结晶特征. 部分水解聚丙烯酰胺(HPAM)降低了重烷基苯磺酸盐(HABS)表面活性剂的临界胶束浓度(cmc), 促进了其胶束化作用; HABS使溶液中HPAM链的刚性增强, 负电吸引能力增强; 二者均会形成模板, 导致结垢样品中的碳酸钙具有不同的形貌特征. 聚丙烯酰胺和表面活性剂的存在未改变结垢样品中碳酸钙的层状生长特征.     

Experimental Study of the Effect of Strong Alkali on Lowering the Interfacial Tension of Oil/Heavy Alkylbenzene Sulfonates System

Experimental studies were conducted to explore the fundamental mechanisms of alkali to lower the interfacial tension of oil/heavy alkylbenzene sulfonates (HABS) system. Sodium hydroxide was used as the strong alkali chemical to investigate the interfacial tension (IFT) of oil/HABS system. The influences of salt and alkali on the interfacial activity were studied by the measurement of interfacial tension and partition coefficient. Moreover, the alkali/surfactant solutions were measured by dynamic laser scattering. The results showed that compared with the salt, the function of alkali to lower the interfacial tension and improve partition coefficient is more significant. The micelles formed by surfactants could be disaggregated because of adding alkali, so the size of micelles decreases and the number of mono‐surfactants increases, then more surfactant molecules move to the interface of oil/surfactant system and the adsorption of surfactants at oil‐water interfaces increases, which can lead to the decrease of IFT.     

Thermal analysis of polysiloxanes, aromatic polyimide and their blends

Low molecular weight poly(dimethylsiloxane) and poly(methylphenylsiloxane) were synthesized and blended with polyimide (PI) at its precursor poly(amic acid) stage. FTIR analysis has proven the retention of polysiloxanes in polyimide after the ultimate curing of blends. Differential scanning calorimetric analysis was performed on polysiloxanes to elucidate the structures present in polymers while thermogravimetric analysis (TGA) was performed on polysiloxanes, polyimide as well as their blends to evaluate the thermal stability and to analyze the effect of polysiloxane incorporation in blends. Blends have shown synergistic improvement as compared to neat polyimide.     

Synergistic effect of compatibilizer and sepiolite on the morphology of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene succinate) blends

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBS) with different PHBV/PBS weight ratios (100/0, 75/25, 50/50 and 0/100) were elaborated by melt mixing. The morphological investigation of the different samples, in comparison with that of neat PHBV and neat PBS, pointed out that PHBV/PBS blends form a biphasic system over the whole composition range. Low amount of compatibilizing agent (5 wt%), obtained by grafting maleic anhydride (MA) onto PHBV, i.e. PHBV-g-MA, was used for improving the miscibility between the two components of the blend. The incorporation of a fibrous filler as the sepiolite, easily dispersible in a polymer matrix, was also investigated. The morphology of the different blends as well as the evolution of their material properties were discussed in terms of the sepiolite and compatibilizing agent contents. The dispersion of PBS in the PHBV matrix markedly became finer with incorporation of sepiolite and PHBV-g-MA, due to enhanced interactions between the components. This paper highlighted a synergistic effect induced by the presence of both compatibilizer and sepiolite leading to an improved miscibility of the two blend components. The resulting properties were correlated with the morphology observed for the different blends.     

Characterization of aroma active compounds in fruit juice and peel oil of Jinchen sweet orange fruit (Citrus sinensis (L.) Osbeck) by GC-MS and GC-O

Gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry (GC-O) were used to determine the aromatic composition and aroma active compounds of fruit juice and peel oil of Jinchen sweet orange fruit. Totals of 49 and 32 compounds were identified in fruit juice and peel oil, respectively. GC-O was performed to study the aromatic profile of Jinchen fruit juice and peel oil. A total of 41 components appeared to contribute to the aroma of fruit juice and peel oil. Twelve components were the odorants perceived in both samples. The aromatic compositions of fruit juice were more complex than that of peel oil. Ethyl butanoate, beta-myrcene, octanal, linalool, alpha-pinene, and decanal were found to be responsible for the aromatic notes in fruit juice and peel oil. Nineteen components have been perceived only in the juice and ten compounds were described as aromatic components of only the peel oil by the panelists. These differences lead to the different overall aroma between fruit juice and peel oil.     

三次采油用重烷基苯磺酸盐表面活性剂的协同效应

三次采油用重烷基苯磺酸盐表面活性剂的协同效应     

Synergistic Effect of Graphdiyne-based Electrocatalysts

The synergistic effect can help improve the electrocatalyst performances by combining the advantages of individual components. In particular, such an effect has been more important in the atomic catalysts. In this review, we have summarized the synergistic effect of N, X co-doping graphdiyne[X=B, S, F or transition metal(TM)] electrocatalysts and graphdiyne-based dual-atom catalyst(GDY-DAC). In general, the synergistic cooperation between two different dopants in co-doped GDY and adjacent active sites in GDY-DAC not only promotes their catalytic activity but also greatly enhances the thermodynamic stability of the catalysts. For the N, X co-doping GDY electrocatalysts, doping the heteroatoms like boron, sulphur, phosphorus, and fluorine with nitrogen can further tune the charge density distribution and electronic structure. Meanwhile, the electron exchange between two doping atoms and GDY substrate has been discussed, where the TM-based GDY-DAC is a very promising catalyst for electrocatalysis. More importantly, electronic interactions between different elements on GDY have been carefully discussed. In the end, we have also supplied perspectives to the future developments of the GDY-based electrocatalysts.     

Molecular weight dependence of phase behavior of PEO/P(EO‐b‐DMS) blends: Application of Sanchez‐Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide‐block‐dimethylsiloxane) (P(EO‐b‐DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO‐b‐DMS) blends were obtained by turbidity method. Based on Sanchez‐Lacombe lattice fluid theory (SLLFT), the adjustable parameter, (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced. The calculated binodals with those modified combining rules show good agreement with the experimental data. Furthermore, the calculated volume changes during mixing decrease with increasing molecular weight of PEO, and the relationship between the volume changes and temperature is quite different for the mixtures with different molecular weight of PEO. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 452–459, 2008