Sodium alginate-polyvinyl alcohol/polysulfone (SA-PVA/PSF) hollow fiber composite pervaporation membrane for dehydration of ethanol-water solution

Using polysulfone （PSF） hollow fiber ultrafiltration membranes as the substrate, sodium alginate （SA） and polyvinyl alcohol （PVA） blend solutions as the coating solution, and maleic anhydride （MAC） as the cross-linked agent, SAPVA/PSF hollow fiber composite membranes were prepared for the dehydration of ethanol-water. The effects of different sodium alginate concentration in the coating solutions and different operating temperatures on pervaporation performance were investigated. The experimental results showed that pervaporation performance of the SA-PVA/PSF composite membranes for ethanol-water solution exhibited a high separation factor although they had a relatively low permeation flux. As SA concentration in SA-PVA coating solution was 66.7% and the operating temperature was 40 ℃, SA-PVA/PSF hollow fiber composite membrane （PS4） had a separation factor of 886 and flux of 12.6 g/（m^2·h）. Besides, SA-PVA/PSF hollow fiber composite membranes （PS3 and PS4） were used for the investigation of the effect of ethanol concentration in the feed solution on pervaporation performance.

STRUCTURE AND PROPERTIES OF COMPOSITE POLYURETHANE HOLLOW FIBER MEMBRANES

Composite polyurethane(PU)-SiO_2 hollow fiber membranes were successfully prepared via optimizing thetechnique of dry-jet wet spinning,and their pressure-responsibilities were confirmed by the relationships of pure water flux-transmembrane pressure(PWF-TP)for the first time.The origin for this phenomenon was analyzed on the basis of membranestructure and material characteristics.The effects of SiO_2 content on the structure and properties of membrane wereinvestigated.The experimental results indicated that SiO_2 in membrane created a great many interfacial micro-voids andplayed an important role in pressure-responsibility,PWF and rejection of membrane:with the increase of SiO_2 content,theability of membrane recovery weakened,PWF increased,and rejection decreased slightly.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.

PREPARATION OF POLYVINYLIDENE FLUORIDE/POLYVINYL DIMETHYLSILOXANE COMPOSITE HOLLOW FIBER MEMBRANES AND THEIR SEPARATION PROPERTIES

Microporous polyvinylidene fluoride(PVDF)hollow fibre membranes were spun using the dry-wet phaseinversion method.By means of dip-coating technique,a uniform coating with thickness of around 5-12 μm of polyvinyldimethylsiloxane(PVDMS)was formed on the surface of porous PVDF hollow fibers.The structural parameters of PVDFsubstrate membrane were estimated by gas permeation test.Using N_2/O_2 as the medium,the separation properties ofPVDMS-PVDF composite hollow fiber membranes were also evaluated experimentally.The experimental data of bothpermeability and selectivity are in good agreement with the theoretical results predicted by the presented pore-distributionmodel.In order to obtain the compact composite membrane free of defects by the dip-coating technique,the thickness ofPVDMS skin must be higher than 5 μm.

Fabrication of a Polyamide/Polysulfone Hollow Fiber Composite Membrane

With microporous polysulfone hollow fiber as the substrate, a polypiperazine amide nanofiltration composite membrane was prepared by interfacial polymerization in trimesoyl hexane solution as oil phase and piperazine aqueous solution as water phase. The conditions of the preparation, such as concentrations of monomer solutions, reaction time and temperature, annealing treatment, etc., were investigated. The hollow fiber composite herewith obtained showed high performance with water fluxes over 40 L·m -2·hr -1 and MgSO4 rejection of 93% under a pressure of 0.40 MPa.

Fabrication of polymer/fluoride-containing salts blend composite membranes for CO_2 separation

Poly （N,N-dimethylaminoethyl methacrylate）-poly （ethylene glycol methyl ether methacrylate） （PDMAEMA-PEGMEMA） and cesium fluoride （CsF） were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone （PSf） hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU （1 GPU=10-6 cm3 （STP）/（cm 2 s cmHg））,and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride （KF）,due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization （IP） procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber ultrafiltration （UF） membrane. A hollow fiber composite membrane with good performance was prepared and studied by PT-IR and scanning electron microscopy.

二醛交联PVA/PAN复合膜的渗透汽化脱水性能

探索了渗透汽化脱水用PVA/PAN复合膜的二醛交联处理方法 ,以质量分数为 95%的乙醇水为脱水对象 ,在 70℃下的测试结果为 :用乙二醛处理时 ,分离因子约为 60 0 ,渗透通量约为 1 50 g/ (m2 ·h) ;用戊二醛处理时 ,分离因子约为 2 0 0 ,渗透通量约为 2 0 0 g/ (m2 ·h) ;用对苯二甲醛处理时 ,分离因子约为 4 60 ,渗透通量约为 2 80 g/ (m2 ·h) .研究中还发现二醛的分子大小和结构对交联后膜性能有一定影响 .

PVA/PAN 渗透汽化复合膜的制备与分离性能研究(Ⅰ)——膜制备及处理条件的选择

制备出了ＰＶＡ／ＰＡＮ渗透汽化复合膜，活性分离层ＰＶＡ的厚度为１～１０μｍ，并将其用于乙醇－水混合物的分离．结果表明，热处理条件能显著影响ＰＶＡ／ＰＡＮ复合膜的渗透通量、渗透选择性和分离指数．通过实验确定了最佳的热处理温度和时间．

中空纤维PVA/PAN复合膜填料的乙醇水溶液精馏性能

以乙醇/水溶液为分离对象,中空纤维PVA/PAN复合膜作为精馏填料,考察了不同膜组件的传质分离效率。实验结果表明:各种组件的分离效率均随塔釜加热功率的增加而减小;和大多数中空纤维膜接触器一样,其总传质系数Ky随中空纤维膜组件填充密度φ的增加而减少;相比于传统精馏填料而言,用中空纤维膜做精馏填料分离乙醇水溶液的分离效果更好,可以在常规填料不能操作的液泛线以上进行操作。当塔釜加热功率为120 W,45根中空纤维膜封装在内径为1.6 cm玻璃管中的传质单元高度(HTU)为5.64 cm。

戊二醛交联PVA/PAN复合膜渗透汽化性能的实验研究

研究了戊二醛交联时间对PVA/PAN复合膜分离性能的影响,并用于乙醇水溶液的分离。结果表明,交联处理存在着最优时间。对应于最优交联时间的膜,当料液中乙醇质量分数(wE)为962%,料液温度(t)为70℃时,渗透通量(Jt)为337(g·m-2·h-1),分离因数(αW/E)为3897。进一步考察了料液质量分数为30%～983%,料液温度为50～78℃时,交联膜的分离性能。

Preparation of PFSA/PSf hollow fiber composite membranes with recovered PFSA for the pervaporation separation of EtOH/H_2O

Perfluorosulfonic acid/Polysulfone(PFSA/PSf) hollow fiber composite membranes have been prepared by dip-coating method using PSf ultrafiltration(UF) membrane as substrate with recovered PFSA.The composite membranes were applied to the pervaporation separation of 95% ethanol(EtOH)/H2O mixture.SEM images show that the thickness of the PFSA skin layer of the composite membranes is about 2 μm,much thinner than those of other PFSA composite membranes revealed in the literatures.Effects of annealing temperature,coating solution concentration and counter-ions of PFSA on the pervaporation performances of the composite membranes were investigated.The total flux decreases and separation factor increases with the increase of annealing temperature.The highest permeation flux of 3230 g m-2 h-1 and a separation factor of 5.4 is obtained for the composite membrane annealed at 80°C.The lowest permeation flux of 396 g m-2 h-1 and a separation factor of 27.7 is obtained for the composite membrane annealed at 160°C.The permeation performances of the PFSA/PSf composite membrane are evidently influenced by the counter-ions of PFSA.The flux sequence of the PFSA/PSf composite membranes with different counter-ions is H+】Li+】Ca2+】Mg2+】Na+】K+】Ba2+】Fe3+】Al3+,and the separation factor sequence is H+【Li+【Al3+【Na+【Mg2+【Ca2+【K+ 【Ba2+【Fe3+.The apparent activation energy △Eapp values of the composite membranes with different counter-ions were calculated by Arrhenius law.The sequence of △Eapp values for the membranes with monovalent counter-ions is Li+】Na+】K+.There are very little variations of △Eapp values between the composite membranes with three divalent counterions(Mg2+,Ca2+ and Ba2+),and the △Eapp values of the composite membranes with two trivalent counterions(Fe3+ and Al3+) are relatively high.

PVA与PAN复合膜分离乙醇-水溶液的渗透汽化放大试验

在渗透汽化放大试验装置上，针对乙醇水体系，考察了板框式膜组件的结构合理性和大面积复合膜的稳定性，研究了不同料液流量、料液浓度和料液温度对膜分离性能的影响。实验结果表明，大膜分离性能稳定，膜分离性能在料液流量为０２～０８０Ｌ／ｓ的范围内基本不变，并且总渗透通量及水通量的对数值与料液浓度、料液温度的倒数分别呈线性关系；超薄板框式膜组件设计合理，结构紧凑，有效地抑制了膜料液侧的浓差极化。

中空二氧化硅粒径对PAN纤维膜隔热性和柔软度的影响

为了探究隔热填充物中空二氧化硅(SiO_(2))粒径大小对静电纺丝制备的纤维膜导热系数和柔软度的影响,设计制备不同粒径的中空SiO_(2)微球;采用单轴静电纺丝的方法将中空SiO_(2)填充于聚丙烯腈(PAN)纤维膜中,制备中空SiO_(2)微球聚丙烯腈(PAN)复合纤维膜。利用扫描电子显微镜、透射电子显微镜、热常数分析仪等仪器对中空SiO_(2)微球形貌、复合纤维膜的形貌、导热系数和柔软度进行观察、测试和分析。结果表明:自制中空SiO_(2)微球、粒径均匀、形貌规整,且在纤维内部具有良好的分散性;少量添加中空SiO_(2)微球,即可以显著提高复合纤维膜的隔热性能,在同等体积含量下,减小粒径有利于增加复合纤维膜的隔热性能。与纯聚丙烯腈纤维膜导热系数0.0480 W(m·K)相比,填充了130 nm中空SiO_(2)微球的复合纤维膜导热系数为0.0359 W(m·K),降低了25%。且中空SiO_(2)微球粒径小,可以使复合纤维膜保持更高的柔软性。

Electrokinetic and permeation characterization of hydrolyzed polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane

PAN membrane and hydrolyzed PAN membranes with the same pore size were used to investigate the relationship between the electrokinetic property and permeation performance by streaming potential measurement and ion exchange technology. SEM and FT-IR/ATR spectra were employed to analyze the reaction and the presence of the amide groups. The thickness of the polyacrylic acid (PAA) layer on the membrane surface measured by ion-exchange titration technology increased with the reaction time, and that on membrane hydrolyzed for 50 min could reach 10.8 nm. Streaming potential measurement was used to study the influence of the carboxylic and nitrile group on the membrane surface on their separation property. Zeta potential measured in pure water had close relationship with the permeation property. This measurement also proved that there was a maximum zeta potential between zero and the concentration tested. For the ionization or dissociation of the carboxylic group on the membrane surface, treated membranes had a more flexible zeta potential range than that of the untreated membrane in the pH range of 3-9. They were all negative in pure water and 1 g·L-1 KCl solution, while the membranes hydrolyzed for 30 min and 50min had IEPs at pH 5.5 and 6.1 in 1 g·L-1 MgCl2 solution. Special inflection points of all the membranes were observed in AlCl3 solution for the positive colloid structure of Al(OH)3.

界面聚合法制备低压中空纤维纳滤复合膜

现有中空纤维纳滤膜在实际应用中能耗较高.采用干湿法纺丝技术制备聚砜(PSf)中空纤维超滤膜作为基膜,分别选用哌嗪(PIP)和均苯三甲酰氯(TMC)为水相单体和有机相单体,通过界面聚合工艺的优化,成功制备了低压中空纤维纳滤膜.用扫描电子显微镜和原子力显微镜对膜表面形貌进行表征,用傅里叶变换红外光谱仪和X射线光电子能谱仪分析膜表面的化学结构和元素组成,测试了复合膜的表面水接触角、Zeta电位、截留分子量和孔径分布,研究了单体浓度、界面聚合反应时间以及测试压力对复合膜性能的影响并确定了最佳的工艺条件.结果表明,优化的低压中空纤维纳滤膜具有低交联度的聚酰胺功能层,在0.2 MPa的测试压力下,纯水通量达到(16.0±0.4)L/(m^(2)·h),对质量浓度为1 g/L的盐溶液的截留率为Na_(2)SO_(4)(94.2%±0.9%)>MgSO_(4)(92.2%±0.9%)>MgCl_(2)(51.0%±0.5%)>NaCl(9.5%±0.3%),表现出优异的Na_(2)SO_(4)/NaCl选择性.

分离有机/有机混合物的PVA、CA系列膜及其渗透汽化性能研究(Ⅱ)成膜条件对渗透汽化性能的影响

用溶剂完全蒸发法制备了PVA复合膜 .经对MTBE/MeOH混合物的分离实验得到了PVA复合膜的最佳成膜条件 ,即 :铸膜液中PVA、马来酸浓度分别为 7%、3% ,热处理温度130～ 15 0℃ .在 1%～ 2 %丙酮水溶液中浸泡处理 4～ 8h ,CTA中空纤维RO膜被改性成渗透汽化膜 .CTA中空纤维膜的分离性能优于其它醋酸纤维素系列膜 。

PTFE/PAN共混中空纤维膜的制备与性能

以聚丙烯腈(PAN)为成膜载体,由聚四氟乙烯(PTFE)分散乳液通过干-湿法纺丝制得PTFE/PAN共混中空纤维膜。利用红外光谱(FT-IR)研究了烧结前后中空纤维膜的化学变化,热失重(TGA)分析了中空纤维膜的热稳定性,并采用场发射扫描电镜(FESEM)观察了不同烧结温度的中空纤维膜形貌。结果表明:在预氧化烧结过程中PAN发生了环化反应,生成耐热的梯形结构,提高了中空纤维膜的耐热性;随着烧结温度的升高,生成的点纤结构尺寸明显增加,中空纤维膜的力学强度显著提高。

纺丝工艺与PAN/CA中空纤维超滤膜性能的关系

研究了干－湿法纺丝工艺参数对聚丙烯腈／二醋酸纤维素（ＰＡＮ／ＣＡ）中空纤维超滤膜性能的影响．结果表明，随着填充液压力的升高，挤出速率的增大，以及干纺程的增加，中空纤维膜的孔隙率、平均孔直径和水通量增加，截留率下降．内、外凝固液浓度对膜性能有不同的影响．在总拉伸倍数一定的情况下，改变第一二级拉伸，可有效调节中空纤维的性能．

凝固条件对PVDF/PVA共混中空纤维膜结构及性能的影响

采用干湿法纺丝工艺制备聚偏氟乙烯(PVDF)/聚乙烯醇(PVA)共混中空纤维膜,讨论凝固条件对膜结构及性能的影响,旨在选择适当的凝固条件,制备性能较优的PVDF/PVA共混中空纤维膜。结果表明:凝固浴为液氮时,孔结构非常致密;凝固浴为水时,随凝固浴温度升高,外皮层界面孔数量较少但尺寸增大,且由裂缝状转变为圆孔状,靠近外层的指状孔延长,孔结构变疏松;凝固浴温度升高,水通量增大,卵清蛋白截留率降低;较高的凝固浴温度有利于PVDF结晶和拉伸强度的提高。