界面聚合中空纤维正渗透膜的制备和表征

以聚砜为原料,通过浸没沉淀法制备中空纤维基膜,然后采用界面聚合法制备出中空纤维正渗透膜。考察了制膜参数、基膜结构和FO性能三者之间的关系。结果表明基膜的厚度为影响FO性能的主要因素之一。基膜的厚度越厚,FO过程中渗透效率越低。制得PSF中空纤维正渗透膜的厚度为0.129 mm,断裂拉伸力为2.48 N,FO通量为10.3 L·m-2·h-1,逆向盐扩散性能为0.15 g·L-1。     

基于纳米纤维膜支撑层正渗透复合膜制备的研究进展

性能优良的正渗透(FO)膜的制备是FO技术研究与应用的关键问题之一。静电纺丝纳米纤维支撑层因其特有的三维孔道结构、高孔隙率、低曲率因子等优点,能有效缓解内浓差极化,提高FO膜性能,近年来已被广泛用于FO膜的制备。介绍了FO的浓差极化产生原理以及评估FO复合膜性能的膜结构参数,回顾了纳米纤维作为正渗透支撑层的发展历程(单一材料、共混材料、纳米掺杂以及表面改性),展望了静电纺丝支撑层的发展趋势。     

四通道中空纤维MFI分子筛膜用于二甲苯异构体分离

采用二次生长法在高机械强度、高装填密度的四通道α-Al₂O₃中空纤维载体(7 cm)上制备MFI分子筛膜，探究了膜合成时间、操作温度、原料分压和吹扫气流量等条件对二甲苯异构体膜分离性能的影响。结果表明，160℃水热合成12 h制得的四通道中空纤维MFI分子筛膜对二甲苯异构体分离性能较优，在150℃、原料分压2 kPa、吹扫气流量20 ml/min时对二甲苯/邻二甲苯分离因子高达878,PX渗透性为2.1×10^-8 mol·m^-2·s^-1·Pa^-1。基于优化的制膜及分离操作条件，进一步将MFI分子筛膜制备于27 cm长的四通道中空纤维载体上，也获得了优异的对二甲苯/邻二甲苯膜分离性能，且所制得的膜材料对该体系的分离可稳定运行100 h以上。为推进中空纤维MFI分子筛膜的批量化制备和传统分离工艺的技术革新奠定了基础。     

新型准对称无机膜的正渗透去除Cd2+的效能

正向渗透(forward osmosis, FO)是一种以溶液渗透压差为驱动力的新型膜技术。课题组在先前研究中使用微界面溶胶凝胶法制备了一种全新的准对称结构无机薄膜(QSTFI膜), 与传统的有机聚合FO膜相比具有更大的优势。本文考察了QSTFI膜分离去除水中重金属Cd²⁺的效能, 讨论了Cd²⁺浓度、提取液浓度以及膜表面带电性对Cd²⁺去除的影响机制。采用扫描电子显微镜(SEM)表征了QSTFI膜的微观形貌, 使用能量色散光谱(EDS)、傅里叶变换红外光谱(FTIR)表征了膜的化学组成, 并使用原子力显微镜(AFM)表征膜表面带电特性。结果表明, QSTFI膜表面带负电荷, 能够与液相主体中的Cd²⁺通过静电引力形成双电层结构, 双电层的Debye厚度越大越有利于膜对Cd²⁺的截留。FO实验测试中原液Cd²⁺浓度为10 mg·L^-1的条件下, QSTFI膜对Cd²⁺截留率超过99%, 水通量最大值可达到69 L·m^-2·h^-1(提取液为2.0 mol·L^-1 NaCl)。本研究为拓展FO技术在含重金属废水处理的潜在应用前景提供了理论依据和指导。     

荷电中空纤维复合膜及其正渗透性能研究

以聚丙烯中空纤维微滤膜为底膜、羧甲基纤维素钠为功能材料、氯化铁为交联剂,采用溶液涂覆-交联工艺制备了表面荷电的中空纤维复合膜,将该中空纤维复合膜用于正渗透(FO)过程,研究了汲取液盐含量、原料液流速等对FO通量的影响。结果表明,制备的荷电中空纤维复合膜可用于FO过程,以蒸馏水为原料液、Na2SO4水溶液为汲取液,采用PRO模式进行FO试验,当原料液与汲取液体积流量均为15 mL/min、汲取液浓度为0.5 mol/L时,FO水通量为12.3 L/(m2.h),盐通量与水通量的比为1.42 g/L。     

UiO-66-NH2与季铵盐协同改性正渗透膜及其对染料废水分离性能

为了提高正渗透(FO)膜对染料的分离与抗污染性能，采用共混相转化法将聚对氯甲基苯乙烯(PCMS)引入聚偏氟乙烯(PVDF)多孔支撑底膜中，经UiO-66-NH₂与PCMS上的氯甲基的亲核取代反应，使UiO-66-NH₂均匀地固定在膜表面，进一步通过改进的界面聚合工艺即在其水相溶液中添加苯基三甲基氯化铵(TMPAC)，制备同时具有高渗透性能和抗污染性的FO复合膜。对支撑底膜和FO膜的结构和性能进行分析表征，并通过FO装置测试FO膜渗透分离和抗污染性能。结果表明，UiO-66-NH₂的引入有效提升了FO膜的亲水性、荷电性及渗透性能，界面聚合工艺中季铵盐的加入极大提升了FO膜的分离和抗污染性能。改性后的FO膜(M2-T)纯水通量可达到22.4 L·m^-2·h^-1，对染料废水中罗丹明6G和橙黄G的截留率可达97.82%和99.84%，经过6 h的罗丹明6G运行后，归一化通量衰减率仅为10.18%，纯水通量恢复率仍有95.66%。     

壳聚糖/聚砜复合中空纤维膜的制备及其CO2/N2分离性能研究

以壳聚糖(CS)为涂层材料,聚砜(PSf)为基膜材料,运用浸渍涂覆的方式制备了壳聚糖/聚砜复合中空纤维膜,考察了壳聚糖质量分数、涂覆时间以及操作温度和压力对CO2、N2的渗透分离性能的影响。结果显示,在聚砜基膜上涂覆壳聚糖材料后,可有效提高CO2/N2分离系数;CO2、N2的渗透速率符合Arrhenius关系式;CO2在复合中空纤维膜中的渗透由溶解-扩散和促进传递两方面主导,而N2的渗透符合溶解-扩散模型。     

聚酰胺复合正渗透膜的制备及其脱盐性能研究

通过溶液相转化法制备四种基膜,然后采用界面聚合法制备不同基膜的聚酰胺复合正渗透(FO)膜,并对其结构与性能进行表征。结果表明,正渗透膜基膜表面开孔率高、孔径分布均匀,且纯水通量大;在基膜中引入聚酯(PET)筛网使其厚度增大、孔隙率和纯水通量降低。基膜材料为聚砜(PSF)时,复合膜聚酰胺分离层较为疏松,以聚偏氟乙烯(PVDF)为基膜材料,形成的分离层较为致密且具有典型峰谷结构,从而使反向盐通量更小。四种复合膜的正渗透纯水通量均大于10 L/m2·h,最高达20 L/m2·h。120 min连续正渗透脱盐实验表明,复合膜截盐率及其稳定性优于商用膜,尤其PET筛网支撑PVDF基复合膜的截盐率基本稳定在97. 5%左右,表现出良好的运行可靠性。     

聚酰胺复合正渗透膜的制备及其脱盐性能研究

通过溶液相转化法制备四种基膜,然后采用界面聚合法制备不同基膜的聚酰胺复合正渗透(FO)膜,并对其结构与性能进行表征。结果表明,正渗透膜基膜表面开孔率高、孔径分布均匀,且纯水通量大;在基膜中引入聚酯(PET)筛网使其厚度增大、孔隙率和纯水通量降低。基膜材料为聚砜(PSF)时,复合膜聚酰胺分离层较为疏松,以聚偏氟乙烯(PVDF)为基膜材料,形成的分离层较为致密且具有典型峰谷结构,从而使反向盐通量更小。四种复合膜的正渗透纯水通量均大于10 L/m2·h,最高达20 L/m2·h。120 min连续正渗透脱盐实验表明,复合膜截盐率及其稳定性优于商用膜,尤其PET筛网支撑PVDF基复合膜的截盐率基本稳定在97. 5%左右,表现出良好的运行可靠性。     

钛中空纤维膜改性及应用研究

采用相转化法制备高致密的钛中空纤维膜后,使用电化学阳极沉积法在其表面负载二氧化钛Ti O₂纳米结构进行改性,并以罗丹明B(Rh B)为模拟有机废水评价其催化降解性能。结果表明,以钛粉(Ti)、N-甲基吡咯烷酮(NMP)、钯(Pd)、聚砜(PS)为铸膜液原料,且NMP:PS=6:1,烧结温度为1000℃制得的高致密钛中空纤维膜,将其浸泡于Ti Cl₃溶液中,在恒电流10m A/cm²、沉积时间10min条件下,可在钛中空纤维膜载体表面负载平整光滑的线状纳米Ti O₂。与纯钛板和纯钛中空纤维膜相比,负载纳米Ti O₂的钛中空纤维膜,对浓度为8mg/L的Rh B溶液的电化学降解速率最快,其降解效率在40min内可达95%。     

Fabrication of innovative forward osmosis membranes via multilayered interfacial polymerization on electrospun nanofibers

Practical application of forward osmosis (FO) membranes is beset by low water flux and vulnerability of selective polyamide (PA) layers. Herein, novel composite membranes were fabricated with multilayered PA via cyclic interfacial polymerization (IP) on electrospun polyethersulfone (PES) nanofiber substrates to realize high performance FO. The membrane fabrication conditions were optimized detailedly with respect to the morphologies, physicochemical properties, and FO performances. It is indicated that the PES concentration has great impacts on the morphology, thickness, and fiber diameter of the electrospun substrates and the optimal concentration is proved to be 26 wt %. After multilayered IP, the membrane thickness, surface hydrophilicity, and mechanical strength increased with IP cycles. The optimized FO membranes with two PA layers show much higher water flux and membrane selectivity compared with the commercial thin film composite membranes, holding great promise for water purification and seawater desalination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47247.     

Thin-film composite forward osmosis membranes with substrate layer composed of polysulfone blended with PEG or polysulfone grafted PEG methyl ether methacrylate

To advance commercial application of forward osmosis (FO), we investigated the effects of two additives on the performance of polysulfone (PSf) based FO membranes: one is poly(ethylene glycol) (PEG), and another is PSf grafted with PEG methyl ether methacrylate (PSf-g-PEGMA). PSf blended with PEG or PSf-g-PEGMA was used to form a substrate layer, and then polyamide was formed on a support layer by interfacial polymerization. In this study, NaCl (1 mol?L⁻¹) and deionized water were used as the draw solution and the feed solution, respectively. With the increase of PEG content from 0 to 15 wt-%, FO water flux declined by 23.4% to 59.3% compared to a PSf TFC FO membrane. With the increase of PSf-g-PEGMA from 0 to 15 wt-%, the membrane flux showed almost no change at first and then declined by about 52.0% and 50.4%. The PSf with 5 wt-% PSf-g-PEGMA FO membrane showed a higher pure water flux of 8.74 L?m⁻²?h⁻¹ than the commercial HTI membranes (6–8 L?m⁻²?h⁻¹) under the FO mode. Our study suggests that hydrophobic interface is very important for the formation of polyamide, and a small amount of PSf-g-PEGMA can maintain a good condition for the formation of polyamide and reduce internal concentration polarization.     

正渗透膜污染影响因素的研究与分析

以海藻酸钠（ALG）为典型有机污染物,采用TFC FO膜,以水通量下降率和污染阻力作为膜污染的评价指标,探究了正渗透（FO）过程中的膜摆向（FO模式和PRO模式）、原料液（FS）和驱动液（DS）的浓度、原料液中Ca²⁺浓度和pH对FO膜污染的影响规律,并提出适宜的膜清洗方案。结果表明,在PRO模式下,膜污染阻力为3.38×10¹¹m^-1,而在FO模式下仅为3.88×10¹⁰m^-1,表明FO模式污染轻;FS或者DS浓度的增大均会导致污染阻力增大,使得污染更加严重;当FS中不含Ca²⁺和含Ca²⁺浓度分别为1mmol/L和2mmol/L时,相较于初始通量,其通量降低率分别15.40%、18.49%和24.93%,当Ca²⁺浓度从1mmol/L增大到2mmol/L过程中,膜污染阻力增大1.6倍;当FS的pH为4.2、7.0和10.7时,水通量降低率依次增加,分别为14.56%、14.82%和18.78%。分别采用去离子水、pH为3.0的HCl溶液、pH为11.8的NaOH溶液以及十二烷基硫酸钠（SDS,pH=11.0）溶液对膜进行清洗,得到SDS溶液清洗效果较好,通量恢复率可达90.70%。     

Developing thin‐film‐composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

A new scheme has been developed to fabricate high‐performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p‐Phenylenediamine and 1,3,5‐trimesoylchloride were adopted as the monomers for the in‐situ polycondensation reaction to form a thin aromatic polyamide selective layer of 150 nm in thickness on the substrate surface, a lab‐made polyethersulfone (PES)/sulfonated polysulfone (SPSf)‐alloyed porous membrane with enhanced hydrophilicity. Under FO tests, the FO membrane achieved a higher water flux of 69.8 LMH when against deionized water and 25.2 LMH when against a model 3.5 wt % NaCl solution under 5.0 M NaCl as the draw solution in the pressure‐retarded osmosis mode. The PES/SPSf thin‐film‐composite (TFC)‐FO membrane has a smaller structural parameter S of 238 μm than those reported data. The morphology and topology of substrates and TFC‐FO membranes have been studied by means of atomic force microscopy and scanning electronic microscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Characteristics and potential applications of a novel forward osmosis hollow fiber membrane

There has been a resurgence of interest in forward osmosis (FO) as a potential means of desalination, dewatering and in pressure retarded osmosis, which Sidney Loeb was advocating over 3 decades ago. This paper describes the characteristics and potential applications of a newly developed FO hollow fiber membrane, which was fabricated by interfacial polymerization on the inner surface of a polyethersulfone (PES) hollow fiber. This FO membrane presents excellent intrinsic separation properties, with a water flux of 42.6 L/m² h using 0.5 M NaCl as the draw solution and DI water as the feed with the active layer facing the draw solution orientation at 23 °C. The corresponding ratio of salt flux to water flux was only 0.094 g/L, which is superior to all other FO membranes reported in the open literature. To evaluate different application scenarios, various NaCl solutions (500 ppm (8.6 mM), 1 wt.% (0.17 M) and 3.5 wt.% (0.59 M)) were used as the feed water to test the performance of the FO membrane. The membrane can achieve a water flux of 12.4 L/m² h with 3.5 wt.% NaCl solution as the feed and 2 M NaCl as the draw solution, suggesting it has good potential for seawater desalination.     

Potential use of nanofiltration like-forward osmosis membranes for copper ion removal

The discharge of industrial effluent containing heavy metal ions would cause water pollution if such effluent is not properly treated. In this work, the performance of emerging nanofiltration(NF) like-forward osmosis(FO)membrane was evaluated for its efficiency to remove copper ion from water. Conventionally, copper ion is removed from aqueous solution via adsorption and/or ion-exchange method. The engineered osmosis method as proposed in this work considered four commercial NF membranes(i.e., NF90, DK, NDX and PFO) where their separation performances were accessed using synthetic water sample containing 100 mg·L~(-1) copper ion under FO and pressure retarded osmosis(PRO) orientation. The findings indicated that all membranes could achieve almost complete removal of copper regardless of membrane orientation without applying external driving force.The high removal rates were in good agreement with the outcomes of the membranes tested under pressuredriven mode at 1 MPa. The use of appropriate salts as draw solutes enabled the NF membranes to be employed in engineered osmosis process, achieving a relatively low reverse solute flux. The findings showed that the best performing membrane is PFO membrane in which it achieved N 99.4% copper rejection with very minimum reverse solute flux of 1 g·m~(-2)·h~(-1).     

Feasibility of using polycarbonate as a substrate of thin film composite membrane in forward osmosis

In the present study, thin film composite (TFC) forward osmosis (FO) membranes with polycarbonate (PC (and polyether sulfone (PES) as substrates were fabricated to investigate the impact of the structural parameters of substrate on the performance of the membranes. Firstly, the substrates were prepared by Loeb-Sourirajan method. Characterization techniques including FESEM, contact angle measurement, pure water flux, gas permeability test, and tensile test were applied to investigate the properties of the substrates. After preparing suitable substrates, active layers were fabricated via interfacial polymerization (IP) technique. The performance and characterization test showed that PC is a relatively hydrophilic polymer with a good property for using as a substrate of FO TFC membrane but as the result of gas permeability test show, this membrane has large surface pore size in comparison with PES membrane. Mean pore size of PC and PES membrane is 378 and 139 nm, respectively. Also, the results show that the effective surface porosity of PC (285, 1/m) is more than PES (213, 1/m) substrate.     

刮刀厚度对聚酰胺正渗透复合膜性能的影响

为考察正渗透过程基膜厚度对膜水通量的作用,有效地提高膜的综合性能,采用浓度2 mol/L的NaCl作为汲取液、去离子水为原料液作为评价系统,考察了刮刀厚度不同对正渗透复合膜性能的影响。结果表明,以筛孔80μm的筛网作为支撑材料,当采用厚度为45μm的刮刀所制备的超滤膜作为支撑材料时,制备所得的正渗透复合膜性能为佳,结构参数S可低至1.086 mm;并具有最好的稳定性以及最佳的污染冲洗恢复效果。     

具有三维聚酰胺脱盐网络结构的无纺布复合正渗透膜

利用间苯二胺（MPD）和均苯三甲酰氯（TMC），直接在聚酯无纺布（NV）织物的多孔空间中进行界面聚合，形成大通量无纺布复合正渗透（NVC-FO）膜。NVC-FO膜在无纺布内部形成的多层次三维（3-D）聚酰胺结构，分布在30~50μm深的聚对苯二甲酸乙二醇酯支撑材料的内部。这种相对松散的有深度的3-D聚酰胺网络，不仅透水表面积大，而且可以避免薄层聚酰胺缺陷导致的高漏盐性，有较低的反向盐通量。进一步研究发现，在一定范围内降低单体质量分数（MPD 1%~0.01%，TMC 0.5%~0.005%），可以形成更宽广的3-D聚酰胺网络结构，在保持较低的反向盐通量的同时得到更高的水通量。使用1mol/L NaCl作为汲取溶液，优化的NVC-FO膜水通量最高可以达到193.54L/(m²·h)，反向盐通量为0.047mol/(m²·h)。采用加压正渗透实验，发现这些高通量NVC-FO膜的盐穿透破裂压力在200~1400Pa之间，而且证实了降低单体质量分数会导致膜的耐压性能显著降低。尽管NVC-FO膜的耐压性能有待提高，但是该研究有可能为构建高脱盐性能的FO膜提供一条新的思路。