Dye removal using hydrophobic polyvinylidene fluoride hollow fibre composite membrane by vacuum membrane distillation

Hydrophobic polyvinylidene fluoride (PVDF) hollow fibre composite membranes were prepared by the dilute solution coating process to build a special surface structure that was similar to the dual micro‐nano structure on the lotus leaf. Poly(vinylidene fluoride‐co‐hexafluoropropene) was chosen as the hydrophobic polymer candidate in dilute solution. Membrane morphology and surface hydrophobicity were evaluated by scanning electron microscopy and dynamic water contact angle measurement. The prepared PVDF hollow fibre membranes were employed to separate dyes (Congo Red and Methylene Blue) from water by vacuum membrane distillation. The effects of operational conditions (feed temperature, vacuum pressure and feed flow rate) on the vacuum membrane distillation performance of different PVDF membranes were investigated. The results indicated that the water contact angle values of PVDF composite membrane surfaces improved from 93.6° to 130.8°, which was mainly attributed to the formation of micro‐nano rods. This structure was similar to the dual micro‐nano structure on the lotus leaf. Under test feed temperature, vacuum pressure and feed flow rate conditions, the dye rejection rate of Congo Red and Methylene Blue by the hydrophobic PVDF hollow fibre membrane remained above 99.5% and 99%, which was higher than that of the pristine PVDF membrane (99% and 98%, respectively). In addition, the hydrophobic PVDF hollow fibre composite membrane showed higher permeation flux under different conditions compared with the pristine PVDF membrane, which was attributed to membrane surface hydrophobicity and the electrostatic interactions between dyes and the PVDF membrane surface.     

膜蒸馏用PDMS/PVDF/PTFE三元共混微孔膜制备

采用浸没沉淀相转化法制备了聚二甲基硅氧烷/聚偏氟乙烯/聚四氟乙烯（PDMS/PVDF/PTFE）三元共混微孔膜,并用于20 g/L NaCl水溶液的膜蒸馏脱盐实验。通过扫描电子显微镜观察以及接触角、膜孔隙率和膜平均孔径分析,研究了PTFE含量对膜结构与性能的影响。结果表明,随着PTFE含量的增加,共混微孔膜断面的指状孔逐渐被海绵状取代,平均孔半径由0.234 μm增加到0.354 μm,膜孔隙率由53.4 %增加到81.3 %;膜下表面与水接触角从118.52 °增加到131.11 °;膜蒸馏过程中通量逐渐增加,截留率先稳定后降低,PTFE含量为40 %（质量分数,下同） 时达最大,为99.99 %,此时膜蒸馏通量达16.60 kg/(m2·h)。     

基于仿生矿化的PTFE中空纤维膜亲水改性研究

由于聚四氟乙烯(PTFE)材料具有强疏水性和极低的表面能,使得PTFE中空纤维膜润湿性差,难以处理水性溶液,限制了其应用过程和领域,因此开展PTFE中空纤维膜亲水化改性研究具有重要的现实意义。利用仿生矿化技术对PTFE中空纤维膜进行表面改性,研究了不同矿化工艺对膜亲水性能的影响,并对改性前后PTFE中空纤维膜的官能团、水通量、气通量、孔径及孔径分布进行了表征。研究表明,仿生矿化能够提高PTFE中空纤维膜的亲水性和水通量,同时由于碳酸钙分子进入膜孔内部,使孔径分布更加均匀,平均孔径和气通量减小。     

Scale-up of NaA zeolite membranes onα-Al2O3 hollow fibers by a secondary growth method with vacuum seeding

NaA zeolite membranes were prepared by secondary growth method on the outer surface ofα-Al2O3 hollow fiber supports. Vacuum seeding method was used for planting zeolite seeds on the support surfaces. Hydrother-mal crystallization was then carried out in a synthesis solution with molar ratio of Al2O3:SiO2:Na2O:H2O=1:2:2:120 at 100 °C for 4 h. Effects of seeding conditions on preparation of hollow fiber NaA zeolite membranes were extensively investigated. Moreover, hollow fiber membrane modules with packing membrane areas of ca. 0.1 and 0.2 m2 were fabricated to separate ethanol/water mixture. It is found that the thickness of seed layer is obviously affected by seed suspension concentration, coating time and vacuum degree. Close-packing seed layer is required to obtain high-quality membranes. The optimized seeding conditions (seed suspension mass concentration of 0.5%–0.7%, coating time of 5 s and vacuum degree of 10 kPa) lead to dense NaA zeolite layer with a thickness of 6–8μm. Typically, an as-synthesized hollow fiber NaA zeolite membrane exhibits good pervaporation performance with a permeation flux of 7.02 kg·m?2·h?1 and separation factor N 10000 for sepa-ration of 90%(by mass) ethanol/water mixture at 75 °C. High reproducibility has been achieved for batch-scale production of hollow fiber NaA zeolite membranes by the hydrothermal synthesis approach.     

Preparation and properties of porous polytetrafluoroethylene hollow fiber membrane through mechanical operations

Porous polytetrafluoroethylene (PTFE) hollow fiber membranes were prepared from fine powder through a series of mechanical operations including paste extrusion, heat treatment, stretching and sintering. In contrast to conventional process, the heat treatment used in this study was performed at 200°C to 330°C (near the melting point) on the PTFE nascent hollow fiber (precursor of membrane). The results showed that the introduction of heat treatment step effectively improved the mechanical properties of precursors, the ultimate stress and strain increased observably with heat treatment temperature, which was beneficial to subsequently stretching precursors to make them porous. Furthermore, the morphological changes and improvement of membrane properties caused by stretching operation were investigated for porous PTFE hollow fiber membrane having finer pore size and higher porosity. The porous microstructure of nodes interconnected by fibrils varied depending on the stretching conditions, such as the stretching temperature, rate, and ratio. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42696.     

载体法制备聚四氟乙烯纤维及烧结工艺研究

以载体法制备出聚四氟乙烯纤维(PTFE)/聚乙烯醇(PVA)初生丝,然后对初生丝进行不同时间的烧结,以除去PVA制得PTFE纤维,对PTFE纤维进行不同程度的拉伸,检测不同烧结时间和拉伸倍数对纤维力学性能的影响。     

Hyperfiltration membranes prepared by radiochemical grafting of styrene onto poly(tetrafluoroethylene). Influence of the size and shape of emulsion particles used to obtain the PTFE film

The hyperfiltration performances of membranes obtained from PTFE films sintered with different granulometric distribution emulsions were studied. It has been possible to show that: (1) large spherical particles lead to high flux, poor rejection membranes, and vice versa for small spherical particles; (2) the particle shape affects the membrane properties. “Stick” shaped particles lead to better rejection properties than the spherical and “fibrillar” ones. An attempt was also made to utilize a PTFE/PMMA porous support to make asymmetric membranes.     

Dewatering of brewer’s spent grain using an integrated membrane filter press with vacuum drying capabilities

Brewer’s spent grain (BSG) is a by-product of the brewing process, rich in fiber, protein and carbohydrates. Its potential application is limited because of high moisture content (80%). This work presents a process for dewatering BSG using two different sets of membrane filter plates in a filter press with vacuum drying: recessive plates with polypropylene membranes and the innovative Rollfit^® plates. A final moisture content of 12-15% was obtained in 15 mm-thick filter cakes, using both types of plates. The dewatering cycle included filtration, membrane-squeezing, and vacuum thermal drying using hot water (~90ºC) as heat source.     

不同中空纤维膜材料对烟气中二氧化硫的吸收性能影响

膜法烟气脱硫能耗低、传质面积大、分离效率高,可以有效地解决传统塔器内的液泛、漏液、夹带等问题。本文采用自制的中空纤维膜接触器,通过改变烟气流量、水流量和水温对比了聚四氟乙烯（PTFE）、聚偏氟乙烯（PVDF）和聚丙烯（PP）这3种中空纤维膜对烟气中二氧化硫的吸收性能,并通过电镜和接触角仪表征,对比了3种膜的参数和疏水性。结果表明：在不同烟气流量、水量和水温下,3种膜的吸收性能都表现为PTFE＞PP＞PVDF,120min时二氧化硫吸收浓度,PTFE最大,是PP的1.68倍,是PVDF的4.62倍;烟气流量的改变对二氧化硫的吸收浓度有显著影响,当烟气流量由60mL/min提高到140mL/min时,120min时PTFE膜二氧化硫的吸收浓度提高了2.14倍;影响膜性能的主要因素为疏水性,PTFE浸泡前后的表面接触角为105°和97°,疏水性远大于PP和PVDF。PTFE中空纤维膜孔径大、孔隙率高,具有极强的疏水性,在烟气脱硫及相关吸收过程中表现出较好的应用前景。     

Air gap membrane distillation on the different types of membrane

Seawater desalination through the air gap membrane distillation (AGMD) process shows merit for its ambient operational conditions and low energy consumption. In this paper nine types of commercially available membranes were characterized to understand the membranes more comprehensively. The density, porosity, mean pore radius, liquid entry pressure (LEP), and contact angle (CA) of the membranes were determined. AGMD experiments were performed for the membranes to investigate the membrane difference on permeation flux and salt rejection. The effects of operating parameters such as temperature, flow rate, and NaCl concentration were studied. The 0.22 μm pore size PTFE membrane showed excellent performance for its higher permeability and higher hydrophobicity than other membranes. The mass transfer coefficients for three types of PTFE membranes were calculated from the results of the experiments.     

减压膜蒸馏浓缩硫酸钠溶液的实验研究

采用减压膜蒸馏技术在较低真空度下浓缩Na2SO4水溶液，研究了真空度、料液温度、料液流速以及料液浓度对膜通量与截留率的影响。结果表明，随着膜下游真空度增加，膜通量增大；料液温度显著影响膜通量；随着料液浓度增加，膜通量严重衰减；实验条件下聚丙烯中空纤维膜表现出很好的疏水性，Na2SO4的截留率接近100%。     

Effect of stretching on continuous oil/water separation performance of polypropylene hollow fiber membrane

In this work, polypropylene (PP) hollow fiber membranes were fabricated by thermal-induced phase separation method. The influence of cold-stretched and hot-stretched treatment on the morphology and permeability of the PP hollow fiber membranes was investigated. The results showed that there were cracks and crystalline particulate structures on the outer and inner surfaces of the stretched PP hollow fiber membranes, which were not isolated but linked together through fiber-like connections. Compared to the original PP hollow fiber membrane, the mean pore sizes, the porosities, the hydrophobicity and water entry pressure of the stretched PP hollow fiber membranes improved significantly. When applied in conjunction with a vacuum system, the PP hollow fiber membranes could continuously remove oils from water surface, and separate surfactant-free and surfactant-stabilized water-in-oil emulsions, as well. The initial kerosene fluxes of the hot-stretched PP hollow fiber membrane were higher than that of the membranes prepared from original PP hollow fibers or cold-stretched PP hollow fibers. The permeate fluxes of the hot-stretched PP hollow fiber membrane for all different emulsion separations were higher than those of the original PP hollow fiber membrane. There could be seen no emulsion droplet in the optical micrographs after separation, indicating that the water-in-oil emulsions were effectively separated in one-step method.     

Simultaneous recovery of phosphorus and nitrogen from liquid digestate by vacuum membrane distillation with permeate fractional condensation

A vacuum membrane distillation(VMD) process with permeate fractional condensation on membrane downstream has been developed for simultaneous recovery of phosphorus and nitrogen from liquid digestate. The polytetrafluoroethylene(PTFE) membrane flux could reach 6000 g·m~(-2)·h~(-1) with the rejection efficiency of total phosphorus(TP) over 0.99, under the condition of flowrate being 120 L·h~(-1) and temperature being 40°C. Membrane fouling occurred with a film of organics and microorganism deposited on the surface of the membrane. Membrane flux could be reversed after the membrane was rinsed by water. Higher feed temperature and flowrate could improve the membrane flux, while hardly affect the rejection efficiency of total phosphorus. The concentration of TP could reach 1600 mg·L~(-1) after membrane distillation, which is about 5 times of that in initial liquid digestate. On the downstream of the membrane, some of the permeate vapor was condensed under the vacuum condition and most of water was collected here. The remaining vapor enriched with total nitrogen(TN) was compressed and pumped to the atmospheric condition to condense. The TN concentration in atmospheric condensate was as high as 7000 mg·L~(-1) with the process separation factor for ammonia being enhanced to 114.     

Numerical simulation studies on heat and mass transfer using vacuum membrane distillation

A general 2D mathematical model was developed to simulate the purification of water from volatile organic compounds (VOCs) via vacuum membrane distillation (VMD) process in hollow fiber membrane contactors. The model was developed for hydrophobic membrane material conditions, taking into consideration axial and radial diffusion in the tube, membrane and compartments of the contactor and was simplified to the two‐dimensional structure with a single porous membrane wall. The simulation has studied the mass and heat transfer of VMD system in the porous media, in which aqueous volatile organic solution was considered as an incompressible and steady fluid. Effect of the downstream pressure on the removal of 1, 1, 1‐trichloroethane (TCA) was studied to validation of simulation results with experimental data that it was obtained from literature. The temperature, Reynolds number, and total mass flux (convective and diffusive) distribution of TCA are determined in the membrane module. POLYM. ENG. SCI., 54:2553–2559, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of poly(dimethylsiloxane)-polytetrafluoroethylene (PDMS-PTFE) composite membrane for pervaporation of chloroform from aqueous solution

Hydrophobic polydimethylsiloxane — polytetrafluoroethylene (PDMS-PTFE) flat-sheet membranes for pervaporation (PV) of chloroform from aqueous solution were successfully fabricated by solution casting method. The structures and the performance of the membranes was characterized by X-ray diffraction (XRD), scanning electron microscope combined with energy dispersive X-ray spectroscopy (SEM-EDXS), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and the tests of contact angle and mechanical properties. The adding of PTFE particles (<4 μm) in the PDMS matrix enhanced the crystallinity, hydrophobicity, mechanical strength and thermal stability of the membranes. The examinations showed that the PTFE filled PDMS membranes exhibited striking advantages in flux and separation factor as compared with unfilled PDMS membranes. All the filled PDMS membranes with different PTFE content showed excellent PV properties for the separation of chloroform from water. When the content of the PTFE additive in PDMS composite membrane was 30 wt%, membrane performance was the best at feed temperature 50 °C and permeate-side vacuum 0.101MPa. For the 30% PTFE-PDMS membrane, with the increase of the feed temperature from 30 to 60 °C, the total, water and chloroform fluxes as well as the separation factor increased, the apparent activation energy (ΔEa) of total, chloroform and water were 21.08, 66.65 and 11.49 KJ/mol, respectively, with an increase of chloroform concentration in the feed from 50 to 950 ppm, total, water and chloroform fluxes increased but the separation factor decreased.     

Ag/PAMAM树形分子纳米复合材料对PTFE膜性能的影响

以第4.0代端氨基聚酰胺-胺型树形分子(G4.0-NH2PAMAM)为模板制备Ag/PAMAM纳米复合材料(Ag·DENPs), 利用了Ag·DENPs与聚四氟乙烯(PTFE)膜表面的氢键作用,通过超声沉积的方法制备出了PTFE-Ag/PAMAM复合膜.通过研究沉积时间对Ag·DENPs在PTFE膜表面沉积量的影响,得到饱和沉积时间是60min,沉积量约为2.32mg.通过UV-vis光谱和SEM对其化学组成和微观形貌进行了表征.复合膜的水接触角为105.3°,较纯PTFE膜降低了23.6°,显著改善PTFE膜表面亲水性.复合膜对水和牛血清白蛋白的通量比纯PTFE膜低,但傅立叶变换衰减全反射红外光谱(FRR)为88.2%,比纯PTFE膜的35.4%高出了52.8%,且对大肠杆菌及金黄色葡萄球菌具有抑菌作用.表明Ag·DENPs的引入可以改善PTFE的抗污染性及抑菌性.     

Separation of liquid mixtures by using polymer membranes. III. Grafted poly(vinyl alcohol) membranes in vacuum permeation and dialysis

A series of poly(vinyl alcohol) membranes were modifed by radiation-induced graft copolymerization with acrylic acid and methacrylic acid monomers. These grafted poly(vinyl alcohol) membranes were then tested for their separation and permeability characteristics in vacuum permeation and dialysis experiments. The permselectivity of the membranes toward methanol and water was studied on a vacuum permeation apparatus at 30, 40, and 50°C. The permeation process was found to be a temperature-activated process. The logarithm of the permeation rate varied linearly with the reciprocal of the absolute temperature. The permeability of the grafted membranes was found to increase with the degree of grafting, with no appreciable selectivity toward water in binary mixtures. The acrylic acid-grafted membranes generally showed greater improvement in permeability than the methacylic-grafted membranes. The permeability of the grafted membranes toward methanol, sodium chloride, urea, creatinine, and uric acid was studied in a dialyzer. In all cases, the grafted membranes showed an improved permeability toward these solutes over the commercial poly(vinyl alcohol) membranes. The dialysis results were then compared with those obtained for dialysis-grade cellophane membranes. For the case of sodium chloride, urea, and methanol, the permeability of the grafted membranes was comparable to that of cellophane. A comparison of commercial and grafted poly(vinyl alcohol) membranes in their permeability toward ionic solutes exhibited somewhat anomalous behavior in that the permeability of the commercial membranes was higher than that of the grafted membranes. This related to the ionic nature of the modified membrane. The permeability coefficients determined in the dialysis experiments were found to be directly related to the degree of hydration of the grafted membrane. This behavior was attributed to changes in the size and shape of voids within the membrane structure.     

Superhydrophobic modification of ceramic membranes for vacuum membrane distillation

The hydrophobically modified ceramic membranes have great potential for energy-efficient membrane distillation.In this work,flat-sheet ceramic membranes with a superhydrophobic surface were fabricated by grafting 1H,1H,2H,2H-perfluorooctyltrichlorosilane or 1H,1H,2H,2H-perfluorodecyltriethoxysilane and followed by ultraviolet irradiation.The surface water contact angle was improved from 46° of original ceramic membrane to 159°,which exhibited a stable and excellent superhydrophobic effect.The modified membranes showed a high flux of 27.28 kg· m-2.h-1 and simultaneously maintained an excellent retention rate of 99.99％,when used in vacuum membrane distillation process for treatment ofa 1 wt％ NaCl (75 °℃) aqueous solution.These results suggested that superhydrophobic modification of ceramic surface is a facile and cost-effective way to achieve higher membrane distillation performance.The superhydrophobically-modified ceramic membrane with an excellent desalination capacity would show considerable potential in practical membrane distillation utilizations.     

Fabrication and characterization of a novel Nafion-PTFE composite hollow fiber membrane

Nafion has been widely used in electrochemistry, but there are only a few reports on its application in other fields, such as, gas separation, even though it exhibits good performance. The primary reason for that is the high cost of Nafion and making a composite membrane with a thin Nafion layer is a potential solution to solve this problem. In this study, a novel Nafion-PTFE composite hollow fiber membrane, which had a thin (~5 μm) and detect-free Nafion layer on PTFE surface, without Nafion filling substrate pores was developed, differing from the reported ones in which Nafion resin was required to impregnate into porous PTFE membrane as thorough as possible to ensure the ion conductivity and operation stability. The surface morphology, crystallite, solubility in ethanol/water mixture, and water uptake of membranes were systemically investigated. The gas permeance tests were also conducted. The permeances of different gasses of prepared composite membranes were significantly enhanced compared with the commercial membranes due to the decrease of Nafion thicknesses, while the selectivity remained the same, verifying the detect-free structure of Nafion layer on PTFE substrate. This study provided a good reference for the preparation and application of low-cost Nafion composite membranes.     

减压膜蒸馏法稀碱液浓缩过程研究

以聚偏氟乙烯疏水膜为材料,采用减压膜蒸馏技术在较高真空度下浓缩硫化钠溶液,研究了各种条件对膜通量的影响.结果表明,当进料温度80℃、真空度为80kPa、流速为0.99m·s~(-1)时,质量分数4.6%的硫化钠溶液VMD膜通量为23.7 kg·m~(-2)·h~(-1);连续运行时,将稀碱液浓缩5倍后,膜通量仍维持在10.6kg·m~2·h~(-1),用稀盐酸清洗后膜通量恢复到初始值的95.6%;浓缩过程产水电导维持在10μS·cm~(-1)以下,脱盐率大于99.99%.