超亲水天然多酚改性膜的制备及其油水分离性能

为研发绿色环保、制备工艺简单的油水分离材料，以单宁酸(TA)和聚乙二醇(PEG)为改性剂，聚偏氟乙烯(PVDF)膜为基底，通过简单浸渍法，制备了超亲水复合膜(TAPE膜)。采用SEM、AFM、FTIR、XPS和接触角测定仪对TAPE膜进行了表征和分析，并考察了TAPE膜的油水分离性能、耐磨性能和稳定性。结果表明，TAPE膜具有多孔微纳米粗糙结构，当TA含量为蒸馏水质量的1.75%时，该膜的水接触角和水下油接触角分别为0°和156°，表现出超亲水性和水下超疏油性。在0.09 MPa工作压力下，TAPE膜分离水包油乳液的膜通量为1146.4 L/(m²·h)，是原始PVDF膜的30倍，该膜对油水混合液和水包油乳液的分离效率均可达99.9%。此外，TAPE膜具有良好的稳定性，膜表面经砂纸(320目)磨损(100 g载重)25次后水接触角仍高达152°。     

用于稳定油包水乳液及控制释放生物活性物质的山梨醇酐聚酯复合体

<正>本发明揭示一种在水包油包水(W/O/W)乳液中的组合物,其组成成分包括:(a)含H2O的连续水相;(b)分散在连续水相间的油相或油壳;以及(c)用于稳定连续水相和油相(或油壳)界面的亲水性聚合物,使其形成水包油(O/W)乳液。油相或油壳包括:(i)油、(ⅱ)分散在油或油壳内的内部水相,以及(ⅲ)一亲脂性山梨醇酐-聚酯复合体,可稳定油和内部水相之间的界面,以形成油包水(W/O)乳液。     

PVA型超亲水-水下超疏油过滤膜油水分离性能研究

稀土萃取分离生产过程中会产生大量的含油废水亟待处理，超亲水-水下超疏油过滤膜为稀土冶炼含油废水带来了新的解决方案。以过滤棉为基材，以富含羟基的聚乙烯醇(PVA)与亲水的纳米二氧化硅溶胶为前驱体，以戊二醛为交联剂制备了PVA型超亲水-水下超疏油过滤膜。接触角测试表明，在空气介质中对水的接触角为0°，在水介质中对油的接触角为155.3°，具备优良的超亲水-水下超疏油性能。对制备的PVA型超亲水-水下超疏油过滤膜进行油水分离实验发现，3次重复实验过滤膜的平均油水分离率为97.5%，膜通量为11.89 L/(m²·s)，经30次油水分离循环测试，该过滤膜仍具有95.3%的油水分离率和11.06 L/(m²·s)的膜通量，展现了较好的耐久性和稳定性，具有一定的工业推广应用前景。     

兼具乳液分离和染料吸附性能的复合海绵的制备及性能研究

通过两步浸渍法制备了具有水下超疏油和抗油污染性能的SiO₂-CS/SA海绵,该海绵仅通过重力作用就能分离含油废水,对多种油水混合物和含表面活性剂乳液的分离效率分别在99.0%和99.1%以上,通量分别在60 000 L/(m²·h)和1 694 L/(m²·h)以上。此外,该海绵还可同时分离含刚果红染料的乳液,经4次循环之后乳液分离效率仍达99.0%以上,对染料吸附率达94.5%以上。因此,这种环境友好型的海绵材料可以促进功能界面材料的发展,在含染料的乳液分离领域具有潜在的应用前景。     

基于壳聚糖/聚乙烯醇/二氧化钛修饰的硝酸纤维素复合膜研究

通过负压抽滤的方法将壳聚糖(CS)、聚乙烯醇(PVA)与二氧化钛(TiO₂)的修饰液涂覆到纯硝酸纤维素膜的表面,制备硝酸纤维素复合膜,研究膜在微观结构、元素分布与组成、浸润性等方面的性能。结果表明,制备的新型膜具有超亲水/水下超疏油特性,过滤柴油乳液通量为5 867.3 L/(m²·h),除油率为99.4%,在强酸碱性、高盐度环境下的油水分离实验时,过滤通量无明显衰减,除油率可保持98.9%以上,具有优良的稳定性和耐腐蚀性。     

低渗透油藏中油包水乳液的生成及其扩大波及体积的作用

针对低渗透水驱波及效率低的问题,研究了具有扩大波及体积作用的油包水乳液的形成及对驱油效果的影响。乳化剂浓度、油水比以及岩心渗透率是影响水包油乳液向油包水乳液的转变的重要因素。在高浓度条件下(0.5%和0.3%),乳化剂TC-6和原油形成的分散体系以水包油乳液为主。随着浓度降低,水包油乳液转变为油包水乳液并伴随着分散体系粘度的升高。相同浓度条件下,油水比升高也会引起水包油乳液向油包水乳液的转变。质量浓度0.3%条件下,油水比6∶4时,分散体系以水包油为主;油水比7∶3时,水包油乳液转变为高粘度油包水乳液。乳化剂浓度,油水比渗透率低于50.1 m D时,水包油乳液不稳定,容易发生反相形成油包水乳液。低渗透岩心实验表明,具有扩大波及体积功能的乳化剂能够在水驱基础上提高采收率8.9%,明显高于超低界面张力表面活性剂体系提高采收率效果。同时,乳化剂分子量小、粘度低,本身不存在注入性的问题,因此对于低渗透油藏水驱后扩大波及体积、提高原油采收率具有重要意义。     

功能化碳纳米管/SMANa/聚醚砜导电分离膜的制备及性能

为改善聚醚砜(PES)导电分离膜的相容性和分离性能,将碱处理的苯乙烯-马来酸酐共聚物(SMANa)和功能化碳纳米管按照不同质量比与PES共混,使用非溶剂诱导相分离法成功制备功能化碳纳米管/SMANa/聚醚砜导电分离膜,对分离膜的结构、形貌和分离性能进行测试。结果表明：通过碱处理苯乙烯-马来酸酐共聚物,成功制备具有良好分散性的SMANa。当功能化碳纳米管添加量为6 g时,导电分离膜的电阻率达到2.929 97×10⁴Ω·cm,纯水渗透通量达到1 188.1 L/(m²·h),而对牛血清蛋白(BSA)的截留率为91.46%。在通入30 V电压后,导电分离膜对刚果红、甲基蓝染料渗透通量分别达到584 L/(m²·h)和480 L/(m²·h),截留率均达到99.99%。     

低渗透油藏中油包水乳液的生成及其扩大波及体积的作用

针对低渗透水驱波及效率低的问题,研究了具有扩大波及体积作用的油包水乳液的形成及对驱油效果的影响。乳化剂浓度、油水比以及岩心渗透率是影响水包油乳液向油包水乳液的转变的重要因素。在高浓度条件下(0.5%和0.3%),乳化剂TC-6和原油形成的分散体系以水包油乳液为主。随着浓度降低,水包油乳液转变为油包水乳液并伴随着分散体系粘度的升高。相同浓度条件下,油水比升高也会引起水包油乳液向油包水乳液的转变。质量浓度0.3%条件下,油水比<6∶4时,分散体系以水包油为主;油水比>7∶3时,水包油乳液转变为高粘度油包水乳液。乳化剂浓度,油水比渗透率低于50.1 m D时,水包油乳液不稳定,容易发生反相形成油包水乳液。低渗透岩心实验表明,具有扩大波及体积功能的乳化剂能够在水驱基础上提高采收率8.9%,明显高于超低界面张力表面活性剂体系提高采收率效果。同时,乳化剂分子量小、粘度低,本身不存在注入性的问题,因此对于低渗透油藏水驱后扩大波及体积、提高原油采收率具有重要意义。     

三嗪框架聚合物膜用于有机纳滤甲醇/正己烷分离

具备耐各种有机溶剂的微孔聚合物膜在有机纳滤领域逐渐受到重视。采用双氰基单体的超酸催化成环聚合反应，制备微孔框架聚合物薄膜(CTF-BP)，该膜具备良好的力学性能，可耐受甲醇和正己烷等常见有机溶剂。CTFBP膜内大量<1.0 nm的微孔通道使膜具备良好的筛分性能，其截留分子量为550。膜内含有的三嗪结构与羟基具有较强的亲和性，使甲醇的跨膜通量[1.10 L/(m²·h·bar)]显著高于黏度更低的正己烷通量[0.23 L/(m²·h·bar)]。采用纳滤操作将膜用于分离含低浓度甲醇的正己烷溶液[含5%(质量)甲醇的正己烷溶液]，结果显示甲醇/正己烷分离因子最高可达到1485，渗透液的总流量超过3.21 kg/(m²·h)。证实CTF-BP膜有望实现高效甲醇/正己烷分离。     

基于强氢键作用的超分子微纳米涂层改性滤膜

为解决油水分离滤膜循环使用性差的问题,采用超分子鞣酸-聚乙烯醇(TA-PVA)黏结剂黏附鞣酸-铜(TA-CuⅡ)形成鞣酸-聚乙烯醇-铜(TA-PVA-CuⅡ)涂层改性聚偏氟乙烯(PVDF)膜,制备了具有稳定微纳米涂层的超亲水/水下超疏油膜(TA-PVA-CuⅡ@PVDF)。采用SEM、FTIR、XPS对制备的膜进行了表征,对改性前后PVDF膜的表面润湿性、油水分离性进行了测试,考察了二价铜离子改性时间对TA-PVA-CuⅡ@PVDF循环使用性以及涂层耐久性的影响。结果表明,在亲水性TA-PVA-CuⅡ微纳米涂层的作用下,TA-PVA-CuⅡ@PVDF的水接触角和水下油接触角分别可达到0°和151.0°,其对乳化油的分离膜通量和分离效率最高分别可达1169.30L/(m²·h)和99.99%,展现出优异的油水分离性能。二价铜离子改性时间为20min时,TA-PVA-CuⅡ@PVDF循环稳定性和耐久性最佳,具有15次的循环分离次数,并且通量改变率为6.6%。     

Forward-osmosis strategy and chemical cleaning of seawater desalination reverse osmosis membranes

In order to settle the membrane fouling of reverse osmosis membranes in seawater desalination process, this study reported a novel strategy based on forward-osmosis process and discussed the effects of different factors like different cleaning combination among reverse osmosis product, simulated reverse osmosis concentrate and simulated seawater, as well as cleaning time on the membrane permeate flux and salt rejection. For irreversible fouling, the effects of different chemical cleaning agents, immersion time and concentration were also investigated in this study. The results exhibited that the cleaning combination between diluted water and simulated reverse osmosis concentrate possessed the best cleaning performance in the process of forward-osmosis cleaning. Such approach also enhanced normalized flux from 9.48 L/(m²·h·MPa) to 13.6 L/(m²·h·MPa) and enhanced NaCl rejection from 80.59% to 92.80%. Furthermore, the normalized flux was enhanced from 9.48 L/(m²·h·MPa) to 14.3 L/(m²·h·MPa) and NaCl rejection was also enhanced from 80.59% to 96.27% after soaking in 2%(mass) citric acid solution for 2h, soaking with 1%(mass) ethylenediamine tetra-acetic acid tetrasodium salt and 0.3%(mass) sodium tripolyphosphate solution for 1.5 h. According to the result of SEM images and AFM images, the forward-osmosis cleaning strategy could not cause the damage of selective layer of membrane surface and caused the drop of inorganic and organic fouling on the membrane surface. Hence, cleaning fouled RO membranes by such approach could prolong the chemical cleaning cycle and reduce the amount of chemical cleaning agent, which has certain industrial application perspectives.     

正渗透策略和化学清洗海水淡化反渗透膜

为解决海水淡化过程中反渗透膜的污染问题,研究了基于正渗透策略的反渗透产水、模拟反渗透浓水、模拟海水不同的组合清洗和清洗时间对膜通量和截留率的影响。针对不可逆污染,研究了不同化学清洗药剂、浸泡时间、浓度对膜通量和截留率的影响。结果表明,正渗透策略清洗方式中,淡水/模拟反渗透浓水的组合清洗方式效果最佳,其归一化通量从9.48 L/(m²·h·MPa)提升至13.6 L/(m²·h·MPa),截留率从80.59%提升至92.80%。此外,经质量分数为2%的柠檬酸溶液浸泡2 h后,再使用质量分数为1%的乙二胺四乙酸四钠盐和0.3%的三聚磷酸钠溶液浸泡1.5 h,其归一化通量从9.48 L/(m²·h·MPa)提升至14.3 L/(m²·h·MPa),截留率从80.59%提升至96.27%。从SEM和AFM图可以看出,正渗透清洗策略并未对膜表面选择层造成损坏,且可以清洗膜表面的有机污染物和无机污染物,因此,应用这种方法对污染的反渗透膜进行清洗,可延长化学清洗周期,减少化学清洗剂用量,具有一定的工业应用前景。     

有机溶剂纳滤膜的润湿性对渗透和分离性能的影响

有机溶剂纳滤是一种绿色、高效、节能的新型膜分离技术,在回收和处理有机溶剂中具有广泛的应用前景。本文采用浸渍法分别将聚合物聚二甲基硅氧烷（PDMS）、嵌段聚醚酰胺（PEBAX2533）和聚乙烯醇（PVA）与聚砜（PS）超滤基膜复合,制备了3种不同润湿性的聚合物耐溶剂纳滤膜,研究了PDMS/PS、PEBAX/PS和PVA/PS复合膜对甲醇、乙醇、异丙醇、正己烷、正庚烷的渗透性能,考察了3种聚合物膜对伊文思蓝/甲醇溶液的有机溶剂纳滤性能。结果表明,有机溶剂在不同润湿性复合膜的渗透和传递性能与溶剂本身的溶度参数、分子量、黏度和极性等有很密切的相关性,溶剂的分子量、黏度、分子动力学直径越小,在同一极性复合膜中渗透通量越大;对伊文思蓝/甲醇溶液的有机溶剂纳滤分离表明,PDMS/PS和PEBAX/PS复合膜的截留率均可达90%以上,通量分别为 58.0L/(m²·h·MPa)和72.2L/(m²·h·MPa);PVA/PS复合膜的截留率为85.1%左右,通量为57.5L/(m²·h·MPa)。     

脱乙酰基改性乙酸纤维薄膜对乳化油分离及积垢机理的探究

利用静电纺丝制造乙酸纤维素膜（CA纤维膜）,并利用添加TiO₂及脱乙酰基（d-CA）对CA纤维膜进行改性,后续对膜过滤特性、渗透通量、油水乳化液去除效率、反洗特性及积垢机制进行讨究。结果显示,CA纤维膜通过TiO₂及d-CA改性后可以提高膜的热稳定性及亲水性能,并得到稳定的纯水通量和过滤通量;最佳的比例为TiO₂@d-18.5%CA纤维膜,在40kPa跨膜压差、60min的操作条件下,其纯水通量、过滤通量、1g/L油水乳化液去除效率以及反洗后通量分别为824.8L/(m²·h)、(311.3±12.5)L/(m²·h)、93.6%±1.1%、451.5L/(m²·h);另外,添加TiO₂可能导致油水乳化液在膜表面不可逆阻力比例的增加,脱乙酰基改性CA纤维膜则可以降低膜自身阻力及增加可逆阻力的比例,提高CA纤维膜在油水分离方面的潜力。     

鳞片状BiVO4不锈钢网涂层的制备及其在油水分离中的应用

随着石油泄漏事故的频繁发生和工业含油废水的大量排放,现代化工油水分离问题日益突出。具有特殊润湿性的材料可以选择性透过水或油,分离效率高且操作简单而广泛应用于油水分离。本文以不锈钢网为基底,通过液相法可控制备得到具有不同尺寸、排列的BiVO₄纳米片涂层。通过扫描电子显微镜、原子力显微镜、接触角测量仪对其表面形貌与润湿性能进行表征,研究BiVO₄纳米片尺寸和排列对水下疏油性能的影响。结果表明当不锈钢网表面均匀生长着鳞片状BiVO₄,且这些纳米片随机放射排列时,涂层水下油接触角达到了165.1°,倾斜角仅为2.0°,具有水下超疏油性质。将该涂层用于油水混合物的分离,分离效率均在95.0%以上且分离通量最大可达1.4×10⁴L/(m²·h),在油水分离领域展现出巨大的应用潜力。     

SiO2改性聚丙烯纤维棉对油水乳状液的高效分离

近年来,基于特殊润湿性理论制备表面具有微纳米粗糙结构的多孔材料成为油水分离领域研究的重点。为了满足不同环境下对不同形式油-水乳状液高效高通量分离的需求,该研究利用纳米SiO2颗粒对聚丙烯（PP）纤维棉有针对性地亲（疏）水改性,构建了系列不同润湿性和粗糙度的PP纤维棉,探究了不同孔隙度和表面能的PP纤维棉对W/O及O/W型乳状液的分离性能,结果表明,经过亲（疏）水改性后的PP纤维棉对水/正己烷和水/甲苯乳状液的分离效率都高于99.5%,通量高于700 L/(m2·h),并针对不同形式油-水乳状液阐释其相应的分离机制,为后续油-水乳状液分离材料的科学设计和可控制备提供了理论依据。     

PERFORMANCE CHARACTERISTICS OF PIPE BENDS AS METERING DEVICES FOR OIL/WATER MIXTURES

The applicability of pipe bends as metering devices for two-phase oil/water emulsions was investigated. The discharge coefficients were determined for emulsions over a wide range of oil and water concentrations. At low oil concentrations, the emulsions were of oil-in-water (O/W) type. However, at high oil concentrations, the emulsions were of water-in-oil (W/O) type. The inversion point was detected by an in-line conductance cell. A sharp change in the electrical conductance occurred upon inversion of one type of emulsion to another. Three standard long radius elbows with different dimensions and radii of curvature were tested. The results indicate that the single-phase calibration curves (discharge coefficient versus velocity) can be used to predict the flow rate of two-phase oil/water mixtures provided that the mixtures are well-homogenized. There is no observable difference between the discharge coefficients of oil-in-water and water-in-oil emulsions. The measured values of the discharge coefficients for emulsions are reasonably close to the values predicted from the equations proposed in the literature for single-phase fluids.     

The effect of shear and oil/water ratio on the required hydrophile-lipophile balance for emulsification

Required hydrophile-lipophile balance (HLB) values were examined in terms of the nature of kerosene-water, both oil-in-water (O/W) and water-in-oil (W/O), emulsions formed using Span 80/Tween 80 surfactant blends. Both the nature of the emulsification method and the oil/water ratio were critical in determining the resulting emulsion type. Both high- and low-shear conditions were investigated. Under high shear, low internal phase emulsions formed using the surfactant mixtures that corresponded to the required HLB values for emulsification involving kerosene (6 for W/O and 14 for O/W). However, at low shear, high internal phase (concentrated) emulsions resulted. Furthermore, depending on the oil/water ratio, some of the high internal phase emulsions were opposite to the type expected, given the HLB of the surfactant blend used. From these results, it appears that the emulsification technique (applied shear and oil/water ratio) used can be of greater importance in determining the final emulsion type than the HLB values of the surfactants themselves.     

Fouling-resistant Composite Membranes for Separation of Oil-in-water Microemulsions

Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water （O/W） mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., a porous ceramic membrane substrate, a polyvinylidene fluoride （PVDF） ultrafiltration sub-layer, and a polyamide/polyvinyl alcohol （PVA） composite thin top-layer. The PVDF polymer was east onto the tubular porous ceramic membranes with an immersion precipitation method, and the polyamide/PVA composite thin top-layer was fabricated with an inteffaeial polymerization method. The effects of the sub-layer composition and the recipe in the inteffaeial polymerization for fabricating the top-layer on the structure and performance of composite membranes were systematically investigated. The prepared composite membranes showed a good performance for treating the O/W microemulsions with a mean diameter of about 2.41μm. At the operating pressure of 0.4MPa, the hydraulic permeability remained steadily about 190L·m^-2·h^-1, the oil concentration in the permeate was less than 1.6mg·L^-1, and the oil rejection coefficient was always higher than 98.5% throughout the operation from the beginning.     

聚丙烯微孔膜的表面矿化修饰及其亲水性能

为了改善聚丙烯微孔膜(MPPM)的表面亲水性,通过组合多巴胺氧化聚合和交替浸渍矿化修饰技术,在MPPM表面构建了均匀的CaCO₃矿物层,实现了利用CaCO₃矿物对膜表面进行亲水化修饰的目的。采用FTIR、XPS、ESEM、EDX和水接触角对矿化膜表面进行了相应的表征。考察了溶液浓度、浸渍循环次数及聚多巴胺涂覆率等对CaCO₃矿化率的影响。结果证实,CaCO₃矿物均匀地负载在MPPM表面,膜的亲水性因CaCO₃固有的润湿性而明显改善。纯水通量测试结果表明,矿化膜具有强的水渗透能力,纯水通量大(高达6450 L·m^-2·h^-1),渗透阻力小,施加0.01 MPa的外压,水即可透过膜。油水乳液分离研究发现,矿化膜能有效地分离一定范围的油水乳液,水通量大(> 1800 L·m^-2·h^-1),且膜容易用水清洗,展现出理想的油水乳液分离应用前景。