噻唑类表面活性剂的合成研究

以2-氨基噻唑、氯乙酰氯为原料,合成2-(2-氯乙酰胺基)噻唑中间体。中间体分别与N,N-二甲基癸基叔胺、N,N-二甲基十二烷基叔胺、N,N-二甲基十四烷基叔胺、N,N-二甲基十六烷基叔胺反应合成一系列噻唑类表面活性剂。通过单因素实验,考察了反应温度、反应时间及反应原料投料比对目标产物收率的影响。利用1HNMR和IR对目标产物结构进行表征。通过电导率法测得噻唑类表面活性剂的临界胶束浓度(cmc)值分别为1.94×10~(-2)、5.01×10~(-3)、1.62×10~(-3)、4.78×10~(-4)mol/L。     

耐盐抗剪切型聚丙烯酰胺降阻剂的制备及研究现状

总结了部分耐盐、抗剪切改性单体的种类,分析了不同降阻剂的溶解时间、相对分子质量以及用量、矿化度、流速等与降阻率的对应关系,以期为耐盐抗剪切型聚丙烯酰胺降阻剂的制备提供借鉴。研究发现,仅含磺酸基团的聚丙烯酰胺降阻剂在流速小于10 m/s时,降阻率在50%～81.3%之间;而同时含磺酸基团和长链疏水基团的聚丙烯酰胺降阻剂在流速大于10 m/s时,降阻率基本高于70%。在流速较高的条件下,同时含有磺酸基团和长链疏水基团的降阻剂应是今后重点研究方向之一。     

一种新型滑溜水压裂液降阻剂合成与应用研究

减阻剂是滑溜水压裂液的核心添加剂,采用反相乳液聚合法合成了一种新型降阻剂,并以其为主剂,配制了一种滑溜水压裂液体系。考察了降阻剂的各项性能和滑溜水压裂液体系对岩心渗透伤害和裂缝导流能力伤害性能。试验结果表明:降阻剂具有较好降阻性能和携砂性能;该降阻剂配制的滑溜水压裂液对岩心渗透伤害率低、对支撑剂导流能力的伤害率低,对支撑剂导流能力的伤害恢复率达到95.8%;该降阻剂配制的滑溜水压裂液具有低摩阻和高弹性的特点,可以实施大液量、大排量、大砂量的施工。     

疏水缔合聚丙烯酰胺作为滑溜水压裂液减阻剂的应用性能研究

以丙烯酰胺、丙烯酸和2-丙烯酰胺基-2-甲基丙烷磺酸作为亲水单体,再引入疏水单体R-8,使用水溶液聚合,获得了低摩阻、高粘弹性的疏水性缔合聚合物DR-8,用FTIR表征结构,分别通过管路摩阻测试系统和流变仪测试了DR-8在不同条件下的减阻性能及流变性能。结果表明,合成的聚合物与预期产品结构一致,当流速为3 m/s、浓度为1.2 g/L时,DR-8的减阻率为75.5%,具有良好的减阻性能,同时具有良好的黏弹性,能够满足非常规油气藏体积压裂、大排量施工、降低摩阻的要求,而且在载砂量方面明显优于常规滑溜水压裂液。     

疏水缔合聚丙烯酰胺作为滑溜水压裂液减阻剂的应用性能研究

以丙烯酰胺、丙烯酸和2-丙烯酰胺基-2-甲基丙烷磺酸作为亲水单体,再引入疏水单体R-8,使用水溶液聚合,获得了低摩阻、高粘弹性的疏水性缔合聚合物DR-8,用FTIR表征结构,分别通过管路摩阻测试系统和流变仪测试了DR-8在不同条件下的减阻性能及流变性能。结果表明,合成的聚合物与预期产品结构一致,当流速为3 m/s、浓度为1.2 g/L时,DR-8的减阻率为75.5%,具有良好的减阻性能,同时具有良好的黏弹性,能够满足非常规油气藏体积压裂、大排量施工、降低摩阻的要求,而且在载砂量方面明显优于常规滑溜水压裂液。     

新型降阻剂DR-12的研制及应用

在页岩气资源的勘探开发中,为改善滑溜水压裂液的性能,通过优选添加剂及低分子聚合物,合成了滑溜水压裂液使用的降阻剂DR-12,对其降阻性能进行了室内评价试验并优化了滑溜水压裂液配方,试验结果表明其降阻性能良好。为了提高DR-12降阻剂的现场施工适应性,优化了施工工艺,主要包括人工裂缝和压裂施工参数的优选,现场试验取得了良好的效果。     

绿色清洁滑溜水重复利用技术在瓜尔胶返排液中的应用

随着单井压裂规模的加大、压裂井次的增多,压裂返排液的重复利用需求逐渐增多。通过引入速分散、耐矿化度单体,提高降阻剂SLW-1的溶解及耐盐性能,通过加入耐温稳定剂TS-2提高瓜尔胶返排液配置的滑溜水耐温性能。当KCl和CaCl2质量分数为0%～10%时,SLW-1降阻率保持在75%。在室温条件下,SLW-1的溶解时间约为15 s;当硼离子质量浓度为0～40 mg·L~(-1)时,降阻率维持在76%以上;当过氧化物质量浓度为0～60mg·L~(-1)时,降阻率保持在76%～77%之间。SLW-1及瓜尔胶返排液分别配置的滑溜水溶解速度均为15 s,降阻率分别为76.5%、76.2%、76.0%;6 000 s-1剪切5 min,降阻率均为76%以上。SLW-1返排水配置的滑溜水在150℃时,降阻率为76.2%;瓜尔胶返排液配置的滑溜水加入耐温稳定剂TS-2后,在150℃时体系降阻率可以保持在75%;加入TS-2后的瓜尔胶返排水配置的高黏液体在120℃剪切100min,黏度保持在100 mPa·s以上。     

疏水缔合水溶性聚合物P(AM/NaAA/DiAC14)的合成与性能

以双烯丙基胺和1-溴代十四烷为原料成了疏水单体N,N-双烯丙基-N-十四烷基胺(DiAC14);采取前加碱二元胶束共聚-共水解法合成了疏水缔合丙烯酰胺/丙烯酸钠/N,N-双烯丙基-N-十四烷基胺共聚物[P(AM/NaAA/DiAC14)],研究了其在水溶液中的缔合行为.结果表明P(AM/NaAA/DiAC14)缔合行为取决于其Mη的大小、疏水单体摩尔分数及其嵌段长度和分布.     

快速增黏滑溜水降阻剂的研制

滑溜水可以有效降低管内摩阻,在非常规油气田开发中得到广泛应用。以快速增黏、抗高矿化度为核心,为了达到高矿化度返排水重复利用的目的,采用氧化还原体系引发丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)和二甲基二烯丙基氯化铵(DADMAC)水溶液进行三元共聚,得到速溶型快速增黏降阻剂。降阻剂性能测试结果表明:该降阻剂水溶性好,增黏速度快,降阻效率高达60%以上;30 000 mg/L矿化度模拟水下黏度保留率接近50%,降阻率仍在50%以上。     

电化学可逆表面活性剂二茂铁烷基胺的制备及性能

N,N-二甲基二茂铁基甲胺分别与溴代辛烷、溴代十二烷、溴代十四烷和溴代十六烷反应,合成了4种二茂铁表面活性剂:N,N-二甲基二茂铁甲基辛烷基溴化铵(Fc8)、N,N-二甲基二茂铁甲基十二烷基溴化铵(Fc12)、N,N-二甲基二茂铁甲基十四烷基溴化铵(Fc14)和N,N-二甲基二茂铁甲基十六烷基溴化铵(Fc16)1。HNMR与元素分析结果表明,Fc8、Fc12、Fc14和Fc16的分子结构与理论结构吻合,质量分数96%;分别测定了4种化合物在还原态(I+)和氧化态(I2+)的表面张力,结果表明,该化合物在还原态具有良好的表面活性,其临界胶束浓度分别为5.92、0.67、0.46和0.07 mmol/L,仅为相应的直链季铵盐阳离子表面活性剂CMC值的1/40、1/25、1/5和1/15;而在氧化态时表面活性不明显。通过该化合物在氧化态和还原态的表面张力曲线的对比,表明该化合物具有良好的可逆变化能力。因而,可以调节化合物所处的氧化态或还原态,控制其表面活性。     

Using water-miscible nonionic hydrophobic monomer associating HPAM as drag reducing agent

A water-miscible nonionic surfmer (AC-TX100) was synthesized based on Triton X-100 and acryloyl chloride. Then, a terpolymer P(AM/AA/AC-TX100) was synthesized by free radical polymerization in aqueous solution and intended to be used as drag reducing agent (DRA). The DRA was defined to be P(AM_87.32/AA_12.46/AC-TX100_0.22) according to ¹H NMR and elemental analysis, the molecular weight was 2.12 × 10⁶ g/mol according to scattering method. DRA shows excellent performance in drag reduction (DR). The highest DR rate of 76% can be obtained when DRA concentration is 0.023% in fresh water; while in brine containing 3% NaCl, DR rate decreases, and it is necessary to increase the concentration to 0.05% to ensure that DR rate is higher than 70%. SEM and cryo-TEM show that DRA forms a network structure in aqueous solution, and the tightness of this structure has a direct influence on DR performance. Specifically, DRA molecules stretch into the whirlpools generated by water at high flow rates, reducing the quantity and intensity of whirlpools, thereby lowering the energy loss and the friction. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48362.     

Study on properties of hydrophobic associating polymer as drag reduction agent for fracturing fluid

In the paper, the hydrophobic associating polymer ACS-210 was prepared by solution polymerization of acrylamide, acrylic acid, salt-resisting monomer and hydrophobic monomer. Chemical structure and properties of the polymer was characterized by FTIR, TGA and XRD. The rheological property of ACS-210 solution was investigated by rheometer. The frictional resistance of the ACS-210 solutions at different application condition was examined using friction testing system. Results showed that the thermal stability of polymer ACS-210 increases and crystallinity of ACS-210 declines after incorporating of hydrophobic monomer. The viscosity of ACS-210 solution of different concentration decreased with prolonging the shearing time and the retention rate of viscosity is relatively high after long shearing time. The relation curve between the viscosity of polymer solution and shear rate followed the power law model. When the concentration of ACS-210 aqueous solution was less than the critical associating concentrations, storage modulus G’ is less than loss modulus G”, the association was weaker between the molecular chains, and the effective spatial structure did not form. After increasing the concentration of the polymer solution, G’ is more than G”, the degree of association of polymer is stronger. The synthesized polymer has favorable drag reduction effect. The molecular weight is not the only factor to determine drag reduction efficiency. The hydrophobic association can also improve the drag reduction efficiency.     

Water soluble copolymers. 55: N-isopropylacrylamide-co-acrylamide copolymers in drag reduction: Effect of molecular structure,hydration, and flow geometry on drag reduction performance

Non-ionic, hydrophobically associating, water soluble N-isopropylacrylamide-co-acrylamide (IPAM) copolymers have been synthesized and characterized specifically for the study of drag reduction. The drag reduction (DR) performance has been measured with a rotating disk rheometer and a capillary flow apparatus. The DR studies were performed in deionized water, 0.514 M NaCl and 1 M urea. DR efficiency is dependent on copolymer structure, composition, and solvation. Copolymers showing intermediate values of hydrophobic character are found to be the most effective drag reducers. For this copolymer series, IPAM-70 (the copolymer synthesized with 70 mole% N-isopropylacrylamide in the feed) is the most efficient drag reducer. The DR properties of the IPAM copolymers are influenced by hydrophobic associations as well as hydrogen bonding. The effects of salts from the Hofmeister series, cosolvents such as dioxane, and temperature are also examined. Drag reduction performance of the various copolymers is correlated to empirical relationships involving degree of polymerization, second virial coefficient or other solvation parameters, and concentration.     

Thermo‐responsive polymers for drag reduction in turbulent Taylor–Couette flow

The addition of a small amount of high molecular weight polymer to a solvent can substantially decrease friction losses by approximately 80%. This phenomenon known as drag reduction (DR) is used extensively in oil recovery during hydraulic fracturing and in many other applications to reduce the pumping costs. However, because of long chain length, these polymers get adsorbed on the surface of reservoir, diminishing the effectiveness of fracking. In the current study, a thermo‐responsive polymer, i.e., poly(N‐isopropylacrylamide) (PNIPAM) is investigated as a drag reducing agent (DRA), which collapses reversibly above 33 °C known as lower critical solution temperature (LCST), thereby preventing it from getting adsorbed beyond this temperature. Free radical polymerization was used to synthesize the PNIPAM and a Taylor–Couette (TC) setup with a rotating inner cylinder was utilized for measuring the DR. The effect of concentration, Reynolds number (Re), and temperature on DR were studied and a maximum of 50% DR was observed at 400 PPM concentration. PNIPAM demonstrated significant decrease in DR beyond LCST, validating its thermo‐responsive nature that could be beneficial for DR in oil recovery or in providing a control modality to DR technologies.DR versus temperature for PNIPAM solution (500 PPM) at Re = 100,000 demonstrating responsive behavior with temperature © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44191.     

纳米流体对空气与水通过水平管道迟缓两相流的减阻作用的实验研究（英文）

This study investigates the effect of injecting nanofluids containing nano-SiO2 as drag reducing agents (DRA) at different concentrations on the pressure drop of air–water flow through horizontal pipe. The test fluid used in this study was air–water with nano-SiO2 particles at 0.1%–1%mass concentration. The test sections of the experi-mental set-up were five pipes of the same length of 9 m with ID from 0.0127m–0.03175m (0.5 to 1.25 in). Air–water flow was run in slug flow regime under different volumetric flow rates. The results of drag reduction (η%) indicated that the addition of DRA could be efficient up to some dosage. Drag reduction performed much better for smal er pipe diameters than it did for larger ones. For various nanosilica concentrations, the maximum drag reduction was about 66.8%for 0.75%mass concentration of nanosilica.     

疏水缔合聚合物减阻剂的合成及流变性能研究

采用疏水单体FW-12(物质的量比2∶1的丙烯酸十八酯与甲基丙烯酸十六烷基酯混合物)与丙烯酰胺(AM)、丙烯酸(AA)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)聚合得到水溶性疏水缔合聚合物减阻剂FHAPAM。考察了聚合过程放热特点,找出含疏水基团时聚合反应热量变化基本规律,用流变仪测定了FHAPAM水溶液的流变性能;芘探针实验探究了溶液的极性及变化规律;室内减阻实验测试其减阻性能。结果表明:FHAPAM聚合温度受疏水单体摩尔分数影响较大,存在明显的平台区,FHAPAM水溶液受剪切作用表现出强触变性;溶液极性随疏水单体摩尔分数的增加而降低,且第一振动带与第三振动带强度比值I1/I3的比值存在突变点;FHAPAM耐温性强于普通聚丙烯酰胺(PAM);疏水单体摩尔分数不同,储能模量(G')、损耗模量(G″)均表现出特殊性。FHAPAM低浓度时,减阻性能优良,其展现出作为滑溜水压裂液良好的应用前景。     

Drag reduction in co-current down flow packed column using xanthan gum

Drag reduction is one of the most important techniques for reducing energy consumption in a packed bed contactor. The present work involves an experimental investigation on flow regime transition for air-water system with and without drag reducing agent (DRA), two-phase pressure drop, friction factor and drag reduction using xanthan gum as DRA. Drag reduction was quantified from the two-phase pressure drop data. Based on the present observations it was found that the percentage drag reduction increases with an increase in the concentration of DRA and it is only effective in the range of 300 ppm to 800 ppm. The experimental results indicate that a maximum of 80% drag reduction was achievable using xanthan gum (800 ppm) as DRA. Furthermore, the experimental data were validated with the available literature correlations.     

溶剂对聚合物减阻剂流变行为和减阻性能的影响

采用博力飞旋转粘度计测定了减阻剂在不同溶剂中溶液的流变性能,通过减阻剂室内模拟环道评价装置测定了不同溶剂合成的聚合物的减阻率。结果表明,减阻剂属于典型的剪切增稠型非牛顿流体;减阻剂在不同溶剂中溶液的粘度随着温度升高而降低;当环己烷与减阻剂的溶度参数相等时,减阻剂在环己烷中的溶解性能最好。并探讨了剪切增稠流体的减阻机理,分析了不同溶剂合成的减阻剂对减阻性能的影响。     

耐盐型聚丙烯酸钠高吸水树脂的合成研究

以过硫酸铵(APS)为引发剂,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用反相悬浮乳液聚合法合成了丙烯酸(AA)-丙烯酰胺(AM)-2-丙烯酰胺基辛烷基磺酸钠(NaAMC8S)三元共聚高吸水树脂,研究了引发剂含量、交联剂含量、AA中和度对树脂吸液性能的影响。结果表明:磺酸基单体NaAMC8S的加入显著提高了吸水树脂的盐水吸收能力,当引发剂含量为0.2%,交联剂含量为0.02%,中和度为75%,加入NaAMC8S为0.5%时,共聚树脂吸自来水的量为601mL/g,吸0.9%Nacl水溶液的量为154mL/g。     

Correlation of polymerization conditions with drag reduction efficiency of poly(1-hexene) in oil pipelines

High molecular weight with long linear side branches are frequently used in oil pipelines as one of the main classes of drag reducer agents (DRAs). We studied the effects of polymerization conditions, including reaction temperature, monomer concentration and cocatalyst concentration ratio (Al/Ti), on the polymerization yield and molecular weight of the resultant poly(1-hexene) made by Ziegler–Natta catalyst and their consequent effects on the drag reduction efficiency in a loop test. The experimental results verified that the catalyst activity increased from 115 to 220 kgPH/molTi.atm, while the molecular weight of poly(1-hexene) dropped from 2100 to 1030 kDa, as the reaction temperature was increased from 0 to 50 °C. The loop test results also revealed that the highest pressure drop was achieved using the polymer synthesized at 0 °C and by subsequent increase in reaction temperature the pressure drop decreased. Furthermore, the catalyst activity increased from 143 to 262 kgPH/molTi.atm by increasing Al/Ti ratio, while the molecular weight increased up to a maximum level of 1500 kDa at Al/Ti = 143 and decreased at higher cocatalyst contents. Similarly, the results showed the maximum pressure drop of 20 % at Al/Ti = 143. Finally, by increasing monomer concentration, the catalyst activity and polymer molecular weight increased from 75 to 262 kgPH/molTi.atm for the former, and from 700 to 1800 kDa for the latter which resulted in maximum pressure drop by 25 %. Moreover, the pressure drop for each utilized poly(1-hexene) was increased proportionately with DRA’s concentration, and interestingly enough, DRAs were further effective at more turbulent flows with higher Reynolds numbers.