矿化度对疏水缔合聚合物溶液溶解时间的影响研究

疏水缔合聚合物是在亲水的聚丙烯酰胺大分子主链上引入少量疏水基团合成的新型水溶型聚合物。其有耐温耐盐的良好特性。但是疏水基的引入降低了聚合物的水溶性,增加了溶解时间。本文以渤海某油田地层水的离子构成作为参考,通过配制不同矿化度溶液来溶解疏水缔合聚合物,探索矿化度对疏水缔合聚合物溶液粘度及溶解时间的影响,并从原理上解释了出现这些现象的原因。最终发现,随着矿化度升高,疏水缔合聚合物溶液粘度降低,溶解时间增大。这种现象是由于矿化度升高,溶液中电解质增多,溶液极性增强,影响了疏水缔合聚合物分子的展开和缔结。     

缔合型增稠剂的结构、性能及增稠机理研究进展

缔合型增稠剂是一种水溶性聚合物,在临界缔合浓度以上,形成以分子间缔合为主的超分子结构,增大了流体力学体积,因此具有较好的增稠性,是新一代的增稠剂。本文主要介绍了疏水缔合水溶性聚合物的结构及溶液性质,具体讨论了影响疏水缔合水溶性聚合物的增稠性能的多种因素,包括聚合物的结构和组成,分子量,离子基团,温度,剪切速率,表面活性剂。     

疏水缔合聚丙烯酰胺溶液性质研究

用粘度法和核孔膜过滤法研究了实验室自制相对分子质量约1000万的疏水缔合聚丙烯酰胺(HAP)溶液的缔合效应,用粘度计考察了电解质浓度、温度和剪切速率对HAP溶液表观粘度的影响,并与相同测试条件下相对分子质量为1770万的部分水解聚丙烯酰胺3530进行对比。结果表明:HAP溶液在70℃的高温和矿化度为5727的高盐条件下,在1000mg/kg附近存在一临界缔合浓度,在临界缔合浓度以上,HAP溶液粘度迅速增加;而3530不存在临界缔合浓度,粘度增加缓慢。浓度为1250mg/kg的HAP溶液通过核孔膜20mL的过滤时间是347.3min,而相同浓度下3530的过滤时间仅为2.1min。浓度为1000mg/kg的HAP溶液即使在矿化度为30000、70℃的高温、30r/min转速的条件下,粘度仍达到32.8mPa·s,而聚合物3530的粘度仅有4.11mPa·s;当剪切速率增加到140r/min、温度为70℃,用矿化度为5727的模拟采出水配制的HAP溶液的粘度为9.21mPa·s,而3530溶液的粘度仅5.18mPa·s。HAP具有良好的耐温抗盐抗剪切能力。     

微乳液聚合法AM-SMA疏水缔合聚合物的研究

通过甲基丙烯酸十八酯(SMA)与丙烯酰胺(AM)微乳液聚合合成了疏水缔合聚合物,采用红外光谱(FTIR)表征了疏水缔合聚合物的结构,考察了SMA含量、AM含量、聚合物浓度、NaCl浓度以及剪切速率对疏水缔合聚合物溶液表观粘度的影响。结果表明聚合物水溶液临界缔合浓度为0.6g/dL,疏水缔合聚合物表现出较强的盐增粘效应和抗盐性;12%SMA的疏水缔合聚合物水溶液表现出剪切增粘和假塑性流体行为,FTIR谱图初步证实疏水缔合聚合物的结构。     

污水中离子对疏水缔合型聚合物溶液粘度的影响研究

通过开展单因素对疏水缔合型聚合物溶液粘度的影响实验,研究污水中非还原性离子Na~+、Ca~(2+)、Mg~(2+)和还原性离子S~(2-)、Fe~(2+)对疏水缔合型聚合物溶液粘度的影响。单因素实验研究表明,疏水缔合型聚合物溶液粘度保留率为60%时,单因素Na~+含量达到350 mg/L,单因素Ca~(2+)或Mg~(2+)含量达到100 mg/L左右,单因素S~(2-)含量达到6.5mg/L,单因素Fe~(2+)含量达到0.5 mg/L,确定对疏水缔合型聚合物溶液粘度的影响顺序是Fe~(2+)>S~(2-)>Ca~(2+)≈Mg~(2+)>Na~+,一方面,少量的还原性离子S~(2-)、Fe~(2+)对疏水缔合型聚合物溶液粘度影响较大,另一方面污水中非还原性离子Na~+、Ca~(2+)、Mg~(2+)含量较高,对疏水缔合型聚合物溶液粘度的影响也不能忽视。     

改进型疏水缔合聚合物性能的实验研究

在室内对疏水缔合聚合物及一种改进型疏水缔合聚合物溶液的耐温、抗盐及抗剪切性质进行对比实验研究,同时通过放大实验对聚合物溶解的功率消耗、溶解时间及溶液的粘度进行了研究。实验表明:改进型的疏水缔合聚合物更加具有优良的耐温、抗盐及抗剪切的特性。放大实验证实改进型的疏水缔合聚合物具有优良的增粘效应,以及可以降低功率消耗、节约能源,但溶解速率有所下降。     

适用三元污水配制聚合物的初步筛选

针对三元采出污水五高(pH值、水质矿化度、含油悬浮、细菌含量、表面活性剂浓度)特性导致配制聚合物粘度下降回注困难的问题,室内通过增粘性、粘度稳定性、抗盐性等性能对比,在油田现用6种聚合物中初步筛选出适用于三元采出污水配制聚合物,并确定影响配制体系粘度的主要因素,提出了三元污水配制聚合物体系时加入杀菌剂的必要性。     

三元复合驱用新型疏水缔合聚合物性能评价

为探索降低三元复合驱化学剂用量的有效途径,评价了几种新型疏水缔合聚合物的性能。无碱和表面活性剂条件下,疏水缔合聚合物的增粘效果与2500万分子量HPAM相近。三元条件下,由于碱和表面活性剂能够促进聚合物分子链上官能团的疏水缔合作用,使粘度大幅度升高,所以相同粘度条件下,三元体系中的聚合物用量小于无碱和表面活性剂时的聚合物溶液。剪切后,疏水缔合聚合物具有较好的粘度恢复性能,可以实现低粘注入、高粘驱替,有利于在油田开发中应用。该类型聚合物与表面活性剂配伍性较好,可在较宽的碱和表面活性剂浓度范围内达到超低界面张力。与2500万分子量HPAM三元体系相比,在驱油效果相近的情况下,该类型疏水缔合聚合物可降低聚合物用量20%以上。     

长6油层疏水缔合聚合物调剖体系研究

疏水缔合聚合物是目前理想的抗温、抗盐和抗剪切且具有高效增粘性的新型聚合物。疏水缔合聚合物调剖技术通过添加交联剂,使之与缔合聚合物形成三维网状结构体系,可控制成胶时间及强度,改善单纯聚合物体系存在的抗盐性、耐温性、抗剪切性差的问题。本文结合镇泾油田长6油层注聚区块地层情况,通过粘度和浓度关系实验优选出了适于该区块的疏水缔和聚合物调剖体系。驱油实验进一步验证了该调剖体系具有很好的调剖性能,能显著提高油田的产油量或减缓油田的产量递减速度,改善油藏水驱效果。     

新型缔合聚合物ADH溶液性能研究

研究了疏水缔合水溶性聚合物稀溶液的盐增粘性、抗温性、pH值效应,分析了溶液中聚合物与外加表面活性剂的相互作用,并初步研究了剪切速率对聚合物溶液粘度的影响。     

AM_nBS_SSS三元疏水缔合聚合物PAnBS的合成及溶液性能研究

以对正丁基苯乙烯(nBS)、对乙烯基苯磺酸钠(SSS)和丙烯酰胺(AM)为原料,采用自由基胶束聚合法合成了阴离子型三元疏水缔合聚合物PAnBS,用红外光谱法、紫外光谱法以及核磁共振氢谱法对共聚物的结构进行了表征;考察了不同反应条件对共聚物溶液表观黏度的影响,得到了具有较强增黏能力的聚合物合成工艺条件:nBS、SSS和引发剂用量分别为总单体摩尔分数的1.5%、9%和0.1%,总单体和表面活性剂十二烷基硫酸钠(SDS)在溶液中的质量分数分别为25%和6%,反应温度50℃,反应时间10 h。与相对分子质量(简称分子量,下同)1 970万、水解度19.43%的超高分子量部分水解聚丙烯酰胺(HPAM)相比,所得PAnBS在NaCl或CaCl2水溶液中具有更强的增黏能力;PAnBS在淡水或盐水溶液中于80℃下的耐老化性能优于超高分子量HPAM,表现出优良的耐温抗盐性能。     

岔30断块S/P二元复合驱实验研究

针对华北岔30断块90℃高温、地层水矿化度18765.1 mg/L的特点,筛选得到了石油磺酸盐CDS-1与疏水缔合聚合物HNT201-3二元复合体系。0.05%CDS-1/HNT201-3二元复合体系与原油的界面张力可降到10^-2mN/m数量级;当HNT201-3浓度为1250mg/L时,复合体系的表观粘度为23.7 mPa.s。非均质岩心（模拟油层非均质变异系数和平均空气渗透率）驱油试验结果表明,注入驱油体系0.3PV、后续保护段塞0.1PV（聚合物HNT201-3浓度1250mg/L）时,可比水驱提高采收率19.73%OOIP。     

Effect of micro-aggregation behavior on the salt tolerance of polymer solutions

Polymer solution for oil displacement is mostly used in the middle and late stage of water flooding reservoir development, and reservoir groundwater conditions are often one of the main conditions restricting polymer application. Therefore, it is necessary to develop salt tolerance of polymer solutions with different aggregation behaviors, so as to facilitate the synthesis and optimization of suitable polymer systems. The differences in the micro-aggregation behavior of three polymers with different molecular structures were explored. On this basis, the effects of divalent metal cations on the properties of the polymer solutions were analyzed by assessing the micro-aggregation behavior, apparent viscosity, hydrodynamic size, and shear rheological characteristics. The results showed that the linear partially hydrolyzed polyacrylamide (HPAM) was seriously affected by divalent cations, and the viscosity decreased obviously. The aggregation behavior of the polymer changed by hydrophobic association can enhance the salt tolerance of the solution. The hydrophobically modified partially hydrolyzed polyacrylamide (HMPAM) with “chain beam” aggregation behavior has strong intermolecular connection, which enables it to withstand the content of calcium and magnesium ions of 1100 mg l⁻¹. When the content of calcium and magnesium ions exceeds 600 mg l⁻¹, dendritic hydrophobically associating polymer (DHAP) will destroy the interaction between molecular chains, resulting in the decrease of apparent viscosity and hydrodynamic size. For polymer flooding in high-salinity reservoir, salt tolerant polymer system can be constructed by optimizing molecular weight and hydrophobic group content.     

新型表面活性剂疏水缔合聚合物提高原油采收率的性能研究

介绍了渤海海上油田二元复合驱驱油的设计与开发方案,以新型表面活性剂(非离子型表面活性剂:DMES-14、TX-100)和疏水缔合聚丙烯酰胺(HAPAM)为主。二元复合驱驱油体系主要需要双子表面活性剂双十四酸乙二酯双磺酸盐型表面活性剂(DMES-14),疏水缔合聚丙烯酰胺以及取自海上油田平台的回注水。该体系同时对粘度和表面张力进行了研究。结果表明,该体系在不要求浓度的情况下可以达到超低界面张力2.48×10~(-3) m N/m,在油藏中粘度可达到55 m Pa;随后的岩心驱替试验表明,在水驱含水75%的状况下进行二元复合驱驱油效果可提高至38.6%以上。总之,该实验研究提供了非离子表面活性剂与疏水缔合水溶性聚合物驱油体系的实用信息以及可以在渤海海上油田进行大规模应用HAPAM。     

Polymeric and non-crosslinked acid self-thickening agent based on hydrophobically associating water-soluble polymer during the acid rock reaction

Different from traditional crosslinked polymer diverting agents, a polymeric and non-crosslinked acid self-thickening agent (ZPAM) based on hydrophobically associating water-soluble polymer of acrylamide (AM), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (DMC) and N,N′-dimethyl octadecyl allyl ammonium chloride (DOAC) was synthesized. The apparent viscosity variation of ZPAM acid solutions in acid rock reaction and rheological properties of ZPAM spent acid solutions were studied. Results showed that ZPAM acid solutions demonstrated good uninterruptedly thickening ability from low apparent viscosity to high apparent viscosity during the acid rock reaction. Meanwhile, ZPAM spent acid solutions showed good shear resistance, viscoelasticity and high temperature resistance. The thickening mechanism of ZPAM acid solutions during the acid rock reaction was explained by apparent viscosity change, rheological properties of simulative ZPAM acid solutions, and ZPAM aqueous solutions with different concentrations of CaCl₂. The results showed increasing calcium chloride concentration enhanced the hydrophobic association strength of the thickener solution, resulting in increasing solution viscosity, in other words, the self-thickening agent showed excellent salt resistance and acid resistance. In addition, the change of association strength of ZPAM acid solutions during the acid rock reaction was further confirmed via environmental scanning electron micrographs and UV spectrum. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47907.     

疏水改性羟丙基胍胶(Hm-HPG)水溶液黏度行为研究

该文研究了疏水改性羟丙基胍胶(Hm-HPG)水溶液的黏度行为。结果表明:当Hm-HPG水溶液浓度超过临界缔合浓度cac后,溶液表观黏度(ηa)会迅速增加;水溶液中Hm-HPG质量分数为0.4%时,ηa随温度的升高经历升高-降低-平衡的变化过程,在20℃附近出现最大值;水溶液的ηa随NaCl、KCl和CaCl2加入量的增大不断增加,NaCl对溶液ηa增加的贡献最大,KCl次之,CaCl2最弱。当水溶液中Hm-HPG-R16和Hm-HPG-R12质量分数分别高于0.2%和0.3%时,十二烷基硫酸钠(SDS)与疏水聚合物存在着明显的相互作用。     

The solution behavior of hydrophobically associating zwitterionic polymer in salt water

The acrylamide‐based hydrophobically associating zwitterionic polymer was prepared, which was composed of dimethyl‐dodecyl‐allyl ammonium chloride as hydrophobic group and carboxyl betaine 2‐(4‐acrylamido‐propyl‐dimethyl ammonic)‐sodium acetate as functional group. Hydrophobically associating polyacrylamide (HAPAM) was also prepared for comparative study. The behaviors of polymers in pure water and salt solutions were investigated by the means of apparent viscosity test, laser light scattering, atomic force microscope, and fluorescence experiments. The viscosities of polymer solution increased with the increasing of salt concentration, which indicated that the addition of salt resulted in significant antipolyelectrolyte effect in the zwitterionic polymer solution. The results of dynamic laser light scattering experiment also showed that the average hydrodynamic diameters of the zwitterionic polymer molecules increased with the increasing of salt concentration. The network structures had been observed by atomic force microscope and the addition of salt strengthened the formation of network structures. The results of fluorescence experiment showed that the addition of salt could enhance the association of hyrophobically zwitterionic polymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39707.     

矿化度对疏水缔合聚丙烯酰胺溶液性质的影响

研究了NaCl和CaCl2对实验室自制疏水缔合聚丙烯酰胺(HAP)溶液性质的影响。结果表明,ρ(HAP)= 1000 mg/L的溶液,随着ρ(NaCl)的增加,表观黏度先降低后增加再降低,当ρ(NaCl)=3 g／L时,溶液的黏度仍有32．8 mPa·s,远大于部分水解聚丙烯酰胺(3530S型);在0．98 MPa的压力下,HAP溶液通过核微孔滤膜的能力随ρ(NaCl)的增加,逐渐降低。动态光散射实验结果表明,与NaCl相比,ρ(CaCl)=1500 mg／L的溶液对线团尺寸的影响较大,当ρ(Ca2+)=400mg/L时,溶液中聚合物线团直径达到1334 nm,比用去离子水配制溶液的线团直径要大得多。HAP溶液在盐水体系中具有较好的增黏性。     

疏水缔合型聚丙烯酰胺驱油剂的合成与性能评价

针对聚丙烯酰胺的研究现状及其应用中存在的问题,研制出一种抗温、抗盐性能较强,具有一定增粘性能的新型疏水缔合水溶性聚合物。本文通过较为简易的酸醇直接酯化法合成了一种丙烯酸正辛酯,确定了最适宜的合成条件;将该疏水单体与丙烯酰胺采用胶束共聚法合成了一种新型疏水缔合水溶性聚合物,考察了聚合物浓度、盐及温度等对疏水缔合共聚物溶液表观粘度的影响,实验结果表明,合成的聚合物具有良好的耐温抗盐性能。