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.     

新型磺基甜菜碱/聚丙烯酰胺体系表面及界面性能

采用自制的新型磺基甜菜碱两性表面活性剂与相对分子质量2500万的聚丙烯酰胺进行复配,考察了不同温度和矿化度条件下,聚合物对复配溶液表面、界面性能的影响。 采用滴体积法测定了溶液的表面张力,结果表明,加入聚合物使溶液的临界胶束浓度增大,且复配溶液的表面张力大于单独表面活性剂溶液的表面张力。 当聚合物浓度一定,增大溶液矿化度时,体系表面张力增大。 用旋滴型界面张力仪测定了溶液的界面张力,结果表明,增大聚合物浓度,油水界面张力增大,增大溶液矿化度,油水界面张力有所升高。 聚合物质量浓度为1.5 g/L,表面活性剂质量浓度为0.3 g/L时,可使胜利油田孤岛原油和孤东原油的油水界面张力达到超低数量级（10-3 mN/m）。 用分水时间法测定了溶液的乳化性能,结果表明,聚合物浓度增大,分水时间延长,并考察了75、85和95 ℃条件下体系的乳化性能,温度越高,分水时间越短。     

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.     

以油酸为原料的新型生物基支链十七烷基苯磺酸钠的合成及性质

生物基表面活性剂由于其可再生资源和优异的表面/界面性质吸引了越来越多的关注。本文以可再生的油酸为原料,通过四步反应,制备了新型生物基支链表面活性剂,并评价了其表/界面性质、润湿性和生物降解性能。该新型生物基支链表面活性剂为4-（1-十七烷基）苯磺酸钠（9ΦC17S）,依次经过烷基化反应、脱羧反应、磺化反应和中和反应而制得。其化学结构已通过电喷雾质谱、红外光谱和核磁共振波谱得以确认。4-（1-十七烷基）苯磺酸钠展现出良好的表/界面张力,临界胶束浓度（CMC）为317.5 mg·L^-1,CMC处的表面张力为32.54 mN·m^-1,当水溶液中碳酸钠浓度为8.48×10⁴ mg·L^-1、4-（1-十七烷基）苯磺酸钠浓度为8.36×10⁴ mg·L^-1时,油水的界面张力约为10^-2 mN·m^-1。此外,4-（1-十七烷基）苯磺酸钠在生物降解性和润湿性方面也显示出了良好的性能,最终生物降解评分为2.99,0.500 g·L^-1 9ΦC17S溶液的气液固接触角为63.08°。该新型生物基表面活性剂丰富了以可再生资源为原料的生物基表面活性剂的结构多样性。     

介观模拟研究环境因素对油/水界面处十六烷基三甲基溴化铵自组装行为的影响

采用耗散颗粒动力学(DPD)模拟方法在介观层次上模拟了表面活性剂十六烷基三甲基溴化铵(CTAB)在油/水界面的自组装行为,考察了表面活性剂浓度、油水比例以及剪切力等环境因素对表面活性剂界面张力、尾-尾间距离及油水界面厚度的影响。结果发现,油水比例增大可显著降低CTAB存在的油水界面张力,提高CTAB的界面活性;有剪切存在时,表面活性剂在界面的聚集行为明显改变,分子在界面处的排列变得混乱,有序性降低,导致尾-尾间距离减小、界面厚度增加,界面效率显著降低。模拟表明,介观模拟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。     

阴离子孪连表面活性剂的合成及其表/界面活性研究

合成了疏水链长度不同和连接基长度不同的7种系列阴离子孪连表面活性剂,研究了它们的表/界面活性。结果表明,它们有较低的表面张力和临界胶束浓度(CMC),有很好的表面活性。它们的CMC都在10-5~10-6mol/L之间,表面张力在26·5~34mN/m之间。它们有非常好的抗一价、二价盐的能力。除了C16-C2-C16在高于5%的NaCl溶液中会产生析出外,其余孪连表面活性剂都能耐盐20%以上。随着盐浓度的增加,孪连表面活性剂与烷烃间的界面张力逐渐降低,能达到10-3mN/m。与中原油田原油间的界面张力能降低到10-3~10-4mN/m,表明它们可应用于特高矿化度油藏提高采收率。     

两性孪联表面活性剂的合成及溶液性质

用C10～C16脂肪醇与2-氯-2-氧-1,3,2-二氧磷杂环戊烷低温反应生成环状磷酸酯的中间产物,再用N,N-二甲基十二胺在亲核溶剂中65℃下开环反应合成了4种含N 和磷酸根阴离子的两性孪联表面活性剂C10-C12、C12-C12、C14-C12和C16-C12,其质量收率分别为32%、54%、18%和28%。产物的结构通过1HNMR和元素组成分析,表明两性离子表面活性剂C、H、O、N的分析值与理论计算值偏差不超过0.3%。四种表面活性剂的临界胶束浓度(cmc)在0.0072~0.0125mmol/L之间,临界胶束浓度时表面张力(γcmc)依次为23.90、25.61、27.68和36.08mN/m。其中,C10-C12、C12-C12和C14-C12有较好的界面活性,加入盐可以使表面活性剂与烷烃间的界面张力下降,但下降程度有限,不能达到超低界面张力(10-3mN/m)。     

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.     

不同体系中油酸甲酯与烷基苯磺酸盐协同效应研究

研究了表面活性剂/盐/模拟油体系与表面活性剂/碱/模拟油体系中油酸甲酯与表面活性剂协同效应机理.结果表明两种体系中协同效应机理不同.在盐体系中,油酸甲酯主要通过改变油相的等效烷烃碳数(EACN) 影响表面活性剂在油水相分配.而碱体系中,油酸甲酯影响表面活性剂在油水相分配从而影响界面张力；另一方面,油酸甲酯吸附在界面上顶替表面活性剂分子影响界面张力.对于不同结构表面活性剂,两种作用竞争的结果不同.     

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.     

Waste cooking oil as a promising source for bio lubricants- A review

The development of renewable and sustainable products to replace fossil fuels is a key topic in this decade from an industrial, environmental, and scientific perspective. There is an inescapable flow of mineral-based lubricants into the environment due to the increasing use of numerous lubricant types, most of which are mineral-based. Waste cooking oil is another problem, and the disposal of this oil pollutes the environment. Making bio-based lubricant from used cooking oil can solve both of these problems. Lubricating oils that can be created from waste cooking oil are the subject of this article. Bio-lubricants are an attractive alternative to conventional petro-based lubricants because of a number of physical properties, including as biodegradability, high lubricity, and high flash points. Despite this, they are expected to displace petroleum-based lubricants in a range of applications because to their inefficient chemical structure. This allows waste oil to be used as a lubricant while still keeping its tribological and environmental properties through chemical modification. Biodegradable lubricants may benefit from lower prices for waste natural oils, which may help them compete on the market. This article provides a brief introduction of waste cooking oil and its possible use as a bio-based lubricant, as well as the many elements and trends within it.     

生物基环氧树脂及固化剂研究现状

生物基高分子材料以可再生资源为主要原料,它在减少塑料行业对石油资源消耗的同时,也减少了石油化工原料在生产过程中对环境的污染,具有节约石油资源和保护环境的双重功效。桐油和松香是我国两种重要的天然可再生资源,在目前将化工原料逐步转向可再生资源的时代背景下,它们已被广泛应用于高分子材料的合成和改性。生物基热固性树脂是一个意义重大且前景广阔的研究领域,本文就桐油和松香在生物基环氧树脂和固化剂方面的应用进行了系统的综述和展望。     

Interaction between polymer and anionic/nonionic surfactants and its mechanism of enhanced oil recovery

Various experimental methods were used to investigate interaction between polymer and anionic/nonionic surfactants and mechanisms of enhanced oil recovery by anionic/nonionic surfactants in the present paper. The complex surfactant molecules are adsorbed in the mixed micelles or aggregates formed by the hydrophobic association of hydrophobic groups of polymers, making the surfactant molecules at oil-water interface reduce and the value of interfacial tension between oil and water increase. A dense spatial network structure is formed by the interaction between the mixed aggregates and hydrophobic groups of the polymer molecular chains, making the hydrodynamic volume of the aggregates and the viscosity of the polymer solution increase. Because of the formation of the mixed adsorption layer at oil and water interface by synergistic effect, ultra-low interfacial tension (～2.0?×?10^?3 mN/m) can be achieved between the novel surfactant system and the oil samples in this paper. Because of hydrophobic interaction, wettability alteration of oil-wet surface was induced by the adsorption of the surfactant system on the solid surface. Moreover, the studied surfactant system had a certain degree of spontaneous emulsification ability (D50?=?25.04?µm) and was well emulsified with crude oil after the mechanical oscillation (D50?=?4.27?µm).     

Achieving flame retardancy and mechanical integrity via phosphites in bio-based resins

Bio-based flame retardant (FR) resins typically exhibit diminished mechanical properties compared with their petroleum-based counterparts. Recent experiments identified a promising FR phosphorus-bearing vanillin-based epoxy resin, EP2, that exhibited superior thermomechanical properties compared to that of petroleum-based diglycidyl ether of bisphenol A. However, the structure/property relationships of such phosphorus-containing bio-based resins are relatively under-explored and cannot be resolved via experiments alone. Here, molecular simulations are used to explore these relationships for a resin comprising EP2 cured with 4,4-diaminodiphenylmethane. The predicted thermomechanical properties are consistent with experimental observations, and critically, the structural analysis reveals the importance of the pendant phosphite group in the monomer as central to maintaining extensive hydrogen-bonding networks, giving rise to the excellent Young's modulus. This work provides the foundation for knowledge-based strategies to systematically improve the structure/property relationships in FR bio-based epoxy resins.     

有关“环境友好塑料”几个概念的澄清

生物塑料、生物降解塑料、生物基塑料统称为环境友好塑料,但它们三者的侧重点各有不同,既有区别,也有联系,本文对以上三个概念的意义做了详细的解释和澄清。生物塑料注重于生产原料的生物来源性和制造过程的生物技术性;生物降解塑料则注重于它是否可以被生物降解,其原料可以来自于可再生资源,也可来自于石油资源;生物基塑料则关注其生产原料是否来自于可再生资源,而对其是否可以生物降解没有特别要求。     

生物质表面活性剂研究进展

生物质表面活性剂因其原料来源广泛、可再生、无污染等优点,已成为替代石油基表面活性剂的最优选择。目前,生物质类表面活性剂主要以天然脂类、糖类、蛋白质和生物质酚类等物质为原料制备而成,因其特殊的"两亲性"结构,使其具有良好的分散、乳化、增稠、絮凝以及独特的生理等性能,在食品、医疗、日用化学品等行业有较大的应用优势。本文以表面活性剂的发展方向为出发点,综述了以生物质为基础制备表面活性剂的研究进展,展望了生物质表面活性剂的发展方向。     

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.     

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.     

Derivation and synthesis of renewable surfactants

This critical review focuses on the origins and preparation of bio-based surfactants, defined here as non-soap, amphiphilic molecules in which the carbon atoms are derived from annually renewable feedstocks. Environmental concerns and market pressures have led to greater relevance of these chemicals in commercial applications in recent years and extensive research has gone into exploring new classes of surfactants. Highlighted here are examples of bio-based surfactants that are produced on an industrial scale and/or are based on abundant starting materials. The trend of increasing use of renewable resources as starting materials for surfactants is introduced, followed by extensive discussion of the major classes of bio-derived hydrophobes and hydrophiles. Also discussed is the status of research and development with regard to biosynthetically produced surfactants. Finally, concluding remarks address the potential for new surfactant molecular structures as a result of ongoing development in the chemistry of biorefineries, i.e., that the transformation of lignocellulose into fuels is likely to support the manufacturing of new bio-based coproducts (238 references).