表面活性剂驱油效率的影响因素研究

在83℃下测定了3种表面活性剂DL-S、HL-Y/NNR、GZ-16的油水界面张力、乳化能力以及改变油藏岩石润湿性的能力。利用低渗透岩心驱油实验研究表面活性剂的这3种特性对驱油效率的影响。结果表明,表面活性剂的浓度在1 000 mg/L时,DL-S的油水界面张力达到10-3mN/m超低数量级,HL-Y/NNR表现出较为优越的乳化性能,GZ-16具有较好的润湿性能。在驱油实验中,具有最好乳化性能的HL-Y/NNR提高采收率的幅度最大为12.91%,其次为具有超低界面张力的DL-S,相较而言,改变润湿性的能力对驱油效率的影响最小。     

壬基酚聚氧丙烯聚氧乙烯醚磺酸盐应用性能

合成了壬基酚聚氧丙烯聚氧乙烯醚磺酸盐（NPESO-3-4）,采用高效液相色谱法检测了目标产物中原料的含量,同时测定了其表面张力、乳化能力、润湿性及模拟驱油率并与壬基酚聚氧乙烯醚磺酸盐的性能（NPESO-0-4）做了比较。结果表明：与NPESO-0-4相比,NPESO-3-4水溶液降低表面张力的能力略低,但降低表面张力的效率较高。二者与胜利孤东原油之间的界面张力均在10-1 mN?m-1数量级,但NPESO-3-4能将油性表面润湿反转为中间润湿,乳化能力和模拟驱油率明显高于NPESO-0-4,说明含氧丙烯链节的阴-非离子表面活性剂在三次采油中有很好的应用价值。     

复合体系与原油多次乳化过程中油水界面张力变化规律

为进一步了解三元复合驱驱油机理,深入研究复合驱油过程中原油与复合体系两相流体在地层中多次接触乳化过程中界面张力变化规律,在地层温度45℃条件下,开展了一系列不同含水率下强碱三元复合体系与大庆原油多次乳化实验。结果表明,复合体系与原油多次接触乳化后,具有较强地保持超低界面张力的能力;水相分别与上相油和原油间界面张力能够达到超低的乳化次数随含水增加而增加;乳化次数相同时,水相与原油间界面张力低于其与上相油间界面张力;随着乳化次数增加,三元体系与原油间最低界面张力值有先下降后升高的趋势;无论是与原油间界面张力还是与上相油间界面张力达到超低时的乳化次数二元体系都多于三元体系,说明复合驱注入段塞优化时可适当考虑二元体系。     

复合体系与原油多次乳化过程中油水界面张力变化规律

为进一步了解三元复合驱驱油机理,深入研究复合驱油过程中原油与复合体系两相流体在地层中多次接触乳化过程中界面张力变化规律,在地层温度45℃条件下,开展了一系列不同含水率下强碱三元复合体系与大庆原油多次乳化实验。结果表明,复合体系与原油多次接触乳化后,具有较强地保持超低界面张力的能力;水相分别与上相油和原油间界面张力能够达到超低的乳化次数随含水增加而增加;乳化次数相同时,水相与原油间界面张力低于其与上相油间界面张力;随着乳化次数增加,三元体系与原油间最低界面张力值有先下降后升高的趋势;无论是与原油间界面张力还是与上相油间界面张力达到超低时的乳化次数二元体系都多于三元体系,说明复合驱注入段塞优化时可适当考虑二元体系。     

PC-40超分子表面活性剂 制备与室内评价

为改善表面活性剂驱油过程中的表面活性损失及聚驱后储层残余聚合物的再利用,本文利用分子间的共价键作用,进行分子自组装,研制出一种具有高表面活性低损耗的新型表面活性剂PC-40。并对这种新型超分子表面活性剂在界面张力、润湿角、动态吸附量及乳化性等方面进行了室内评价试验。当PC-40浓度达到较高浓度时,油水界面张力达到10~(-2)mN·m~(-1),同时表观粘度有所增大,可通过增稠作用携带注聚后孔道中残余的聚合物增强驱油效率。PC-40溶液具有一定的乳化作用,可使原油充分乳化形成稳定的乳状液;当动态吸附达到平衡,吸附量趋于稳定状态,表面活性损失量相对较低;随着浓度上升,润湿性逐渐向亲油转变,界面张力随之降低,适用于聚驱后进一步提高采收率。     

活性剂对油田污水回注影响研究

通过提高油田污水的循环利用是减少含油污水外排污染的有效途径,但油受到油藏差异性和采油用剂的影响,油田污水回注效率大大降低。为提高中后期油田污水的回注效率,合成一种磺酸盐类的高分子活性剂,以油水界面张力性能、润湿性能、油水乳化能力、洗油率等作为评价指标,从而研究活性剂的分子结构对驱油效率的内在影响机理,为油田回注提供理论与实践参考。     

沥青质模型油/MD膜驱剂溶液的界面张力

从MD膜驱剂与原油界面活性组分沥青质模型油的界面张力出发,考察了作用时间、水相pH、MD膜驱剂质量浓度、盐浓度、沥青质含量、芳香度、温度等对模型油/水界面张力的影响,并根据扩散控制机理解释了动态界面张力初期过程,进一步揭示了MD膜驱油技术的机理。结果表明,沥青质模型油/MD膜驱剂溶液的界面张力先随时间增加而降低,约15min后达到平衡,达到平衡之前的过程基本上符合扩散控制过程;MD膜驱剂的加入并不能改变pH对模型油/水界面张力的影响趋势;在所考察的条件范围内,沥青质模型油/水溶液的界面张力不随MD膜驱剂质量浓度增加而改变,其值约为19 65mN/m;NaCl对界面张力的影响不明显;沥青质质量浓度从0增加到1000mg/L时,模型油/水和模型油/MD膜驱剂溶液的界面张力分别从23 4mN/m和22 0mN/m逐渐下降至20 0mN/m和18 8mN/m;温度从25℃升高到45℃时,模型油/水溶液的界面张力降低;但芳香度从0增加到100%时,其界面张力均从21 0mN/m增加至31 5mN/m。MD膜驱剂是表面非活性物质,在驱油时不存在低界面张力提高采收率的机理。     

可分解香兰素基非离子表面活性剂的乳化性

针对已合成的含缩醛结构的环保型非离子表面活性剂香兰素辛二醇缩醛聚氧乙烯醚(VAEO),研究不同乙氧基链长的VAEO_n(n=6～24)的表面活性及乳化性,并与壬基酚聚氧乙烯醚(NPEO_(10))的表面活性及乳化性作比较。结果表明,随EO聚合度(n)增大,VAEO_n降低表面张力和油/水界面张力的能力下降,对石蜡乳化能力减弱。EO聚合度为6～10的VAEO_n与NPEO_(10)降低表面张力的能力相近,乳化性能也相当。VAEO_n降低油/水界面张力的能力较NPEO_(10)差。采用Material Studio软件模拟分析VAEO_n和NPEO_(10)乳化石蜡的能力,结果表明VAEO_n乙氧基链越长,乳化石蜡重新聚集的速度越快,即乳化性能越差,模拟结果与乳化石蜡分相法的实验结果相吻合。     

界面张力降低速度对乳化及驱油效率影响研究

为深入研究界面张力降低速度对乳化及驱油效率的影响程度,系统考察了相同平衡界面量级条件下,具有不同界面张力降低速度的三元复合驱体系的形成乳化油滴的能力及对人造岩心中提高采收率幅度的影响。实验结果表明,在平衡界面张力都达到10~(-3)mN?m~(-1)量级的前提下,界面张力降低速度过快的体系,由于形成的乳化油滴粒径过小,无法启动小孔道中的油滴,会导致"界面张力窜流现象"即界面张力虽低,采收率提高幅度反而较低,同样,界面张力降低速度过慢的体系,由于形成乳化油滴的数量过少,提高采收率的幅度也较低,只有适宜的界面张力降低速度,才能最大幅度提高采收率。     

表活剂驱油技术

本文调研了国内外分析了表活剂在油田中的应用现状,并在资料分析基础上从低界面张力、润湿反转、乳化、提高表面电荷密度机理、聚并形成油带等方面总括了驱油机理,为表活剂在油田中的应用提供主要依据。     

A Systematic Study of Mixed Surfactant Solutions of a Cationic Ester-Bonded Dimeric Surfactant with Cationic, Anionic and Nonionic Monomeric Surfactants in Aqueous Media

A novel cationic biodegradable dimeric (gemini) surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16), containing an ester-linked spacer was synthesized. Its pure and mixed micellization properties with monomeric surfactants cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl alcohol ethoxylate (20EO) and tert-octylphenol ethoxylate (9.5EO) were investigated by surface tension measurements at 30 °C. The critical micelle concentration (CMC) of 16-E2-16 is well below that of cetyl trimethyl ammonium chloride containing the same number of carbon atoms in the hydrophobic tail per polar head. At different mole fractions of the gemini surfactant, the CMCs of the gemini-conventional binary mixtures were determined and were found to be less than the ideal CMC values in all the cases indicating synergistic interactions. Aggregation number and Stern–Volmer constant, obtained by the fluorescence quenching technique, also support the synergistic behavior of the surfactant systems.     

Guerbet十四醇聚氧乙烯醚硫酸钠的合成与表面活性

以Guerbet十四醇 (C14 GA)为中间体 ,经Williamson反应合成Guerbet十四醇聚氧乙烯醚醇〔C14 GA(EO) nH ,n =1,2 ,4〕 ,再经氯磺酸酯化及NaOH中和 ,得到阴离子表面活性剂Guerbet十四醇聚氧乙烯醚硫酸钠〔C14 GA(EO) nS ,n =1,2 ,4〕。用IR、NMR和元素分析测定了所合成的表面活性剂的结构 ,并利用表面张力法测定了这些表面活性剂水溶液的表面活性。实验结果表明 :所合成的表面活性剂的结构分别为C14 GAEOS (A) ,C14 GA(EO) 2 S(B)和C14 GA(EO) 4 S(C) ;这些表面活性剂其临界胶束浓度CMC(mmol/L) ,在CMC时的表面张力γCMC(mN/m)和Krafft点 (℃ )分别为A :2 5 8mmol/L ,2 7 6mN/m ,5 9℃ ;B :0 80mmol/L ,2 6 4mN/m ,2℃和C :0 12mmol/L ,2 5 3mN/m ,0℃。均比常用的直链阴离子表面活性剂C12 H2 5SO4Na(8.6mmol/L ,4 1 2mN/m ,16℃ )有更低的CMC ,γCMC和Krafft点 ;聚氧乙烯基的引入 ,对降低CMC ,γCMC和Krafft点的效果随氧乙烯基团数目的增多 (由 1增至 4 )而加大。讨论了表面活性剂的结构和表面活性的关系     

Mixed Micellization Properties of Nonionic Fluorocarbon/Cationic Hydrocarbon Surfactants

The physico-chemical properties of mixed surfactant aqueous solutions at various proportions of dodecyltrimethyl ammonium bromide DTAB and undecafluoro n-pentyl decaoxyethylene ether C5F11EO10 have been investigated at 25 °C using surface tension and conductivity measurements. The critical micelle concentration and superficial minimum tension have been experimentally estimated for different DTAB molar fractions. The micellar composition and mutual interaction parameters have been deduced on the basis the theoretical treatments proposed by Clint, Rubingh, and Motomura. The results show a significant synergism effect at about equimolarity of DTAB/C5F11EO10 system probably due to the efficient electrostatic self-repulsion reduction between DTAB cationic head groups related to the presence of the nonionic surfactant in the mixed micelles.     

非离子型Gemini表面活性剂的性质

Gemini表面活性剂具有的优良表面活性,使之有望作为三次采油用的表面活性剂。用界面张力仪及HAAKERS600流变仪研究了非离子型Gemini表面活性剂的表面活性及流变特性。结果表明,25℃下,氧乙基数(EO数)分别为8,10,12的3种非离子型Gemini表面活性剂8-NP-8、10-NP-10及12-NP-12的临界胶束浓度(cmc)值分别为:0.99,0.15和0.032 mmol/L;非离子型Gemini表面活性剂的表面活性及cmc值受电解质的影响较小;氧乙基数为12的非离子型Gemini表面活性剂可以使亲水及亲油固体表面的接触角明显降低,水润湿性增强;非离子型Gemini表面活性剂溶液的粘度随剪切速率增加基本保持不变,呈现出牛顿流体的特性。     

脂肪醇聚氧乙烯醚系列磺酸盐的泡沫性能研究

磺酸盐类阴离子表面活性剂在采油工业中应用广泛,其泡沫性能(起泡性和泡沫稳定性)对采收率影响很大。采用改进的Ross-Miles法对烷基碳数为14、16、18的脂肪醇聚氧乙烯(3)醚磺酸钠(CnH2n 1O(EO)2CH2CH2SO3Na,n=14、16、18)在不同条件下的泡沫性能进行了研究。结果表明,随着疏水基长度增加,表面活性剂起泡性降低,稳泡性增强;十四醇聚氧乙烯(3)醚磺酸钠起泡性最好,十八醇聚氧乙烯(3)醚磺酸钠稳泡性最优;随着温度的上升,3种表面活性剂起泡性增强,稳泡性降低。     

Microemulsion Systems with Rhodium Tris(3-sulfophenyl)phosphine Trisodium Salt Complex for Product Isolation and Catalyst Recycling in the Hydrogenation of Dimethyl Itaconate

Microemulsion systems with the nonionic surfactant p-tert-octylphenoxy polyethoxyethanol (OP9.5EO), the anionic surfactant dioctyl sulfosuccinate sodium salt (DOSS) and the narrow range nonionic surfactant alkyl polyethylene glycol ether (C10EO5) were used as solvent systems in the catalytic hydrogenation of dimethyl itaconate (DMI) catalysed by the water soluble catalyst complex Rh-TPPTS in order to achieve product isolation and catalyst recycling. The DOSS systems, which are more sensitive to the substrate and catalyst addition allowed for the hydrogenation to proceed with an initial hydrogenation rate about three times higher than with the nonionic surfactants, when the surfactant concentration was 15 wt%. Systems with 3 wt% surfactant were used in order to accomplish catalyst recycling. With a biphasic DOSS mixture a turnover number (TON) of 1,200 mol of DMI hydrogenated per mol of catalyst (Rh) was obtained in 3 consecutive runs. A three-phase system for the OP9.5EO mixture allowed the catalyst to be recycled 3 times and a TON of 1,500 in 4 runs was obtained. A TON of 800 in 2 runs was obtained using a three-phase C10EO5 mixture.     

十二烷基苄醇聚氧乙烯醚的合成及性能

以十二烷基苯为原料,经氯甲基化、水解及环氧乙基化等步骤得到平均乙氧基(EO)数为9.5的十二烷基苄醇聚氧乙烯醚(LBAEOn)。分别用FTIR和1HNMR表征了产物LBAEOn的结构特征,并用ESI-MS确定了LBAEOn中的EO分布。以表面张力法测得在25℃时LBAEOn的cmc和γcmc分别为1.83×10-6mol.L-1和39.0 mN.m-1;与脂肪醇聚氧乙烯醚(AEO9)和壬基酚聚氧乙烯醚(NPEO10)相比较,除钙皂分散性能大致相当以外,LBAEOn的表面活性较好、发泡力较低、对正辛醇的增溶能力较强和对帆布的润湿性能较差。     

Surfactant interference on lipase catalysed reactions in microemulsions

The hydrolysis of palm oil with lipase as a catalyst was carried out in two different microemulsion systems. One system was based on a nonionic surfactant, pentaethylene glycol monododecyl ether (C12EO5) and the other system was based on an anionic surfactant, sodium bis(2-ethylhexyl)sulphosuccinate (AOT). The yield of free fatty acid produced by the reaction was found to be much lower in the C12EO5 system compared to the AOT system. Radiochromatography showed that the low yield was due to enzymatic esterification on the nonionic surfactant. Kinetic measurements showed that the reaction rate is about ten times faster in the AOT based microemulsion than in the nonionic system. Differences in the microemulsion structure and interfacial tensions in the two systems were found to be of no significant importance for explaining this difference. Kinetic data of mixed surfactant microemulsions indicated that the observed difference in the reaction rates of the AOT and the C12EO5 microemulsion systems was a consequence of the C12EO5 surfactant competing with the substrate for the active site of the enzyme. The reason why C12EO5 surfactant inhibited the reaction, and AOT surfactant did not, was found to be related to differences in the structures of the hydrophobic part of the surfactant.     

Effects of ethoxylate structure on surfactant properties of ethoxylated fatty methyl esters

In the presence of a surface-modified Al-Mg composite oxide catalyst, ethoxylated fatty methyl esters with different hydrophobic group structures and different chain-lengths of polyoxyethylene were synthesized from fatty methyl esters by direct ethoxylation. Each ethoxylated fatty methyl ester obtained showed a narrow ethylene oxide (EO) adduct distribution. Foaming, ability to lower surface tension, ability to lower interfacial tension, wettability, and dye solubilization were measured. Ethoxylated methyl laurate with about 60 to 70% EO content was found to be the most suitable as a base surfactant for household detergents     

A study on Cationic Surfactants as Drag-Reducing Additives

In this study, we investigated the influence of the number of ethanol (EO) groups of cationic surfactants having one oleyl group on the drag-reducing effect (DR effect). Also the effect of mechanical pumping power on DR effect was experimentally investigated using two experimental setups, a circulation system (with pump) and a pressurized once-through system (without pump). The concluding remarks obtained in this study are: 1. The DR effect strongly depends on the re-formation rate of micelles disrupted mechanically. 2. When increasing the number of EO groups of the DR surfactants from 0 to 2, the available temperature range of large DR effect was shifted lower. But the DR surfactant having three EO groups (EO-3) barely exhibited the DR effect even at the low temperature. This is because the big hydrophilic head of EO groups probably delays the re-formation of micelles disrupted by pumping power. 3. The DR effect was more liable to be influenced by pumping power with a decrease in temperature. This is because it takes a long time to re-form micelles disrupted by pumping power at low temperature.