Fabrication of ZIF-8 membranes on dual-layer ZnO-PES/PES organic hollow fibers by in-situ crystallization

Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.

Recovery of Copper Ions from Wastewater by Hollow Fiber Supported Emulsion Liquid Membrane

Recovery of copper ions from wastewater using a hollow fiber supported emulsion liquid membrane (HFSELM) was studied with LIX984N as carrier, kerosene as diluents, and sulfuric acid solution as stripping phase. Effects of compositions of feed and emulsion liquid phase, flow rates on both sides of membrane, and hollow fiber module parameters were investigated. The stability of the emulsion liquid phase without surfactant and the effect of buffer in the feed phase on the extraction rate were also evaluated. It is found that the stability of the emulsion phase without surfactant is poor. Higher flow velocity gives shorter residence time for the emulsion liquid phase on the tube side, reducing the effect of particle coalescence on the separation process. The extraction rate increases with the increase of feed phase pH, carrier concentration, hydrogen ion concentration in the stripping phase, and ef- fective hollow fiber area. The phase ratio in the emulsion liquid phase has a negative effect on extraction rate. The flow rates on both sides have little influence on the extraction performance of the HFSELM, while buffer addition in the feed solution improves the extraction efficiency.

Hollow fiber liquid-supported membrane technology for enantioseparation of racemic salbutamol by combinatorial chiral selectors

Enantioseparation of salbutamol solute was carried out in liquid-supported membrane by using a polyvinylidene fluoride hollow-fiber module. The enantioselective transport of solute was facilitated by combinatorial chiral selectors, which were dissolved in toluene organic solvent. The effects of molar concentration ratios of salbutamol to combinatorial chiral selectors, and the pH value of buffer solution on enantioseparation were investigated. The results show that when the molar concentration ratio is 2∶1∶1, the maximum separation factor and enantiomer excess are 1.49 and 19.74%, respectively, and the R-enantiomer flux is more than S-enantiomer; the pH value of buffer solution influences the performances of enantioseparartion obviously, and the appropriate range of pH value is 7.07.2.

Transport Study of Cu （Ⅱ） Through Hollow Fiber Supported Liquid Membrane

The transport of Cu(II)from aqueous solutions containing buffer media through hollow fiber supported liquid membrane(HFSLM)using di(2-ethylhexyl)phosphoric acid(D2EHPA)dissolved in kerosene as membrane phase and hydrochloric acid as striping phase was investigated.A set of factors were studied,including tube side velocity,shell side velocity,pH of the feed phase,Cu(II)concentration in the feed phase,buffer media concentration and D2EHPA concentration in the membrane phase.Experimental results indicate that the mass transfer coefficient increases with increasing both carrier concentration in the organic phase and flow rates on the tube side and shell side,and decreases with increasing initial Cu(II)concentration in the feed phase.With increasing pH value and acetate concentration in the feed phase,the mass transfer coefficient reaches a maximum value then decreases.The optimal operating conditions are obtained at pH value of 4.44 and 0.1 mol·L -1 acetic ion concentration in feed phase,and carrier volume fraction of around 10%in kerosene as organic phase.A mathematical model of the transport mechanism through HFSLM is developed.The modeled results agree well with the experimental ones.

MORPHOLOGIES AND GAS SEPARATION PROPERTIES OF MELT-SPUN ASYMMETRIC POLY(4-METHYL-1-PENTENE)HOLLOW FIBER MEMBRANES

Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.

Enhanced gas separation performance of mixed matrix hollow fiber membranes containing post-functionalized S-MIL-53

Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene(PVDF-HFP)hollow fiber membranes were fabricated through a wet spinning process.In order to improve the membrane structure,composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent.The prepared membranes were used for sweeping gas membrane distillation(SGMD)of 20 wt% ethylene glycol(EG)aqueous solution.The membranes were characterized by different tests such as N2 permeation,overall porosity,critical water entry pressure(CEPw),water contact angle and collapsing pressure.From FESEM examination,addition of 3 wt% glycerol in the PVDF-HFP solution,produced membranes with smaller finger-likes cavities,higher surface porosity and smaller pore sizes.Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N2 permeance.The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m^−1.CEPw of 350 kPa and overall porosity of 84% were also obtained for the improved membrane.Collapsing pressure of the membranes relatively improved by increasing the polymer concentration.From the SGMDtest,the developed membrane represented a maximumpermeate flux of 28 kg·m^−2·h^−1 which is almost 19% higher than the flux of plain membrane.During 120 h of a long-termSGMD operation,a gradual flux reduction of 30% was noticed.In addition,EG rejection reduced from 100% to around 99.5% during 120 h of the operation.

A CONDENSED REVIEW ON THE FABRICATION OF HOLLOW FIBER MEMBRANES FOR GAS SEPARATION:HISTORICAL DEVELOPMENT AND TECHNOLOGY CHALLENGES AHEAD

A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical engineers to overcome. There are four major challenges, namely: 1) material selection and synthesis; 2) fabrication of hollow fiber membranes with an ultra- thin dense selective layer; 3) materials against plasticization; and 4) aging. In each area, we summarize the scientific accomplishments and technical difficulties.

Hollow Fiber Supported Liquid Membrane for Separation and Recovery of ^152+154Eu and ⁹⁰Sr from Aqueous Acidic Wastes

Separation and recovery of 152+154Eu and 90Sr from radioactive waste using tracer concentration from active material from waste tank in the ET-RR1 Egypt via hollow fiber supported liquid membrane (HFSLM) were achieved. The Polypropylene was used as supporter to carrier 0.5M Cyanex301/kerosene (bis(2,4,4-trimethylpentyl)dithiophosphinic acid and 0.1MEDTA as stripping of 152+154Eu and 90Sr ions from nitrate medium at pH ~3.6. The separation factor was found to be ~4 for 152+154Eu over 90Sr. The aqueous feed of mass transfer coefficient (ki) and the organic mass transfer coefficient (km) were calculated to be (1.52 and 4.5) × 10﹣2cm/s, respectively. In addition, the mass transfer modeling was performed and the validity of the developed model from experimental data was found to join in well with the theoretical values when the Cyanex301 concentration is higher than 1% (v/v). The number of cycles evaluated for complete separation of 152+154Eu and 90Sr is five cycles.

CHARACTERIZATION OF MIXED GAS PERMEATION THROUGH HOLLOW FIBERS

We have studied the mixed gas permeation in hollow fiber membrane modules using two approaches: namely, the co- current plug flow model and the complete mixing model with the combination of experimental data. Elucidation was made to determine the permeance of CO2 and CH4 and the selectivity of CO2/CH4 in a polyimide hollow fiber membrane permeator It is found that the intrinsic gas separation properties of hollow fibers for mixed gases can be accurately determined based on (1) the cocurrent plug now model, and (2) the complete mixing model with the assumption of averaged retentate concentration of the feed and the retentate outlet.

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.

Polyvinylamine-Based Facilitated Transport Membranes for Post-Combustion CO_(2) Capture:Challenges and Perspectives from Materials to Processes

Carbon dioxide(CO_(2))capture by gas-separation membranes has become increasingly attractive due to its high energy efficiency,relatively low cost,and environmental impact.Polyvinylamine(PVAm)-based facilitated transport(FT)membranes were developed in the last decade for CO_(2) capture.This work discusses the challenges of applying PVAm-based FT membranes from materials to processes for postcombustion CO_(2) capture in power plants and cement factories.Experiences learned from a pilot demonstration system can be used to guide the design of other membranes for CO_(2) capture.The importance of module and process design is emphasized in the achievement of a high-performance membrane system.Moreover,the results from process simulation and cost estimation indicate that a three-stage membrane system is feasible for achieving a high CO_(2) purity of 95 vol%.The specific CO_(2) capture cost was found to significantly depend on the required CO_(2) capture ratio,and a moderate CO_(2) capture ratio of 50%presented a cost of 63.7USD per tonne CO_(2) captured.Thus,FT membrane systems were found to be more competitive for partial CO_(2) capture.

Evaluation of a mathematical model using experimental data and artificial neural network for prediction of gas separation

In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network

以氢溴酸为吸收剂的气态膜法脱氨过程研究

研究了以氢溴酸为吸收剂的气态膜法料液脱氨过程。该过程通过使用聚四氟乙烯(PTFE)或聚丙烯(PP)中空纤维微孔疏水膜制作的膜接触器,从含氨水溶液中脱除/回收氨并相应获得溴化铵副产品.研究了料液中氨浓度、料液中电解质浓度、料液表面张力和吸收液pH等操作条件对传质性能的影响,检验了低表面张力料液对PTFE和PP膜组件性能稳定性的影响.实验结果表明,在提供了最大传质系数的吸收液低pH下氢溴酸的挥发性并没有影响PTFE和PP膜组件的操作稳定性.基于传质机理的数学模型可以描述料液浓度、流速、吸收液pH对总传质系数的影响;料液中的高浓电解质减弱了渗透蒸馏效应,例如当料液中溴化钠质量分数为15%时,氨在吸收完成液中的富集倍数高达41.25.在连续运行的6个月内,PTFE膜组件对使用挥发性氢溴酸作为吸收剂来处理低表面张力的料液表现出了良好的性能稳定性,而PP膜组件的总传质系数在10 d内下降了65%.本研究为气态膜技术处理低表面张力的含氨料液或废水并副产溴化铵的工业化应用提供了基本实验数据和基础理论分析.

Racemic ofloxacin separation by supported-liquid membrane extraction with two organic phases

Based on chemical thermodynamic theory, racemic ofloxacin is separated in chiral sys-tems by hollow fiber liquid-supported membrane technology combining with countercurrently frac-tional extraction. The two chiral solutions containing L-dibenzoyltartaric acid and D-dibenzoylta- rtaric acid in 1-octanol, flow through the lumen side and the shell side of fibers, respectively. The solution which flows through the lumen side of fibers also contains racemic ofloxacin. The wall of hollow fibers is filled with an aqueous of 0.1 mol/L Na2HPO4/H3PO4 buffer solution of pH = 6.86 containing 2 mmol/L of cetyltrimethyl ammonium bromide for 48 h. The fairly polar ofloxacin can cross the membrane back and forth, but dibenzoyltartaric acids cannot cross it. Fractional chiral extraction theory, mass transfer performance of hollow fiber membrane and enantioselectivity are investigated. Mathematical model of R/S = 0.96e0.03NTU for racemic ofloxacin separation by hollow fiber extraction, is established. The optical purity for ofloxacin enantiomers is up to 90% when 11 hollow fiber membrane modules of 22 cm in length in series are used.

几种新型的支撑液膜组件的结构型式

本文介绍四种新型支撑液膜组件的结构型式和特点。它们分别是：中空纤维夹芯型膜组件、管式一中空纤维混合式膜组件、板式夹芯型膜组件和框式隔板夹芯型膜组件。

中空纤维支撑液膜技术处理含铜废水

重金属废水的处理在环境保护和重金属资源综合利用方面都受到广泛的关注。采用中空纤维支撑液膜技术,用CuSO4水溶液模拟工业含Cu(II)废水,二(2-乙基己基)磷酸(D2EHPA)/煤油为液膜相,盐酸为接受相,研究了液膜相组成、两相流速、流动方式等因素对中空纤维支撑液膜过程传质性能的影响。结果表明,料液相在管程流动时的传质通量大于料液相在壳程流动时的传质通量,传质通量随着管、壳程两相流速的增大及液膜相中载体浓度的增加而增大。模拟实验结果表明,中空纤维支撑液膜技术可同时实现废水中Cu(II)的去除与浓缩,处理效果好。废水中Cu(II)的去除率达97%以上,富集液中Cu(II)浓缩倍数达5倍以上。

中空纤维支载离子液体液液微萃取法检测环境水体中的三氯生

三氯生(5-Chloro-2-(2,4-dichlorophenoxy)phenol,TCS)是一种新型环境水体污染物,具有潜在的生态与健康风险,因此发展合适的分析方法来检测水环境中这类化合物极其必要。本研究以l-辛基-3-甲基咪唑六氟磷酸离子液体([C8MIM][PF6])为萃取剂,基于中空纤维的离子液体液液微萃取方法,结合HPLC/UV用于环境水样中TCS的分析测定;通过对各参数(萃取剂、供体相的体积、供体相pH值、离子强度、萃取时间等)的优化在最优条件下(样品相体积为50 mL,pH值2,盐浓度为0.2 mol/L,200 r/min振荡萃取8 h),获得了较高的富集倍数(907倍)、较低的检出限(0.05μg/L,RSD=7.4%,n=6)和较好的线性范围(0.1～100μg/L);以4种环境水样加标实验对方法的准确性进行评估,其回收率可达94.2%～108.5%(RSD=5.5%～8.0%,n=6);本方法可广泛应用于环境水体中痕量TCS的分析检测。

基膜表面处理对反渗透复合膜性能的影响

采用表面活性剂十二烷基磺酸钠(SDS)和弱极性试剂异丙醇(IPA)作为聚砜基膜表面改性试剂,观察其对中空纤维反渗透复合膜性能的影响.结果表明:选择不同处理剂在一定浓度和时间下处理基膜,所制备复合膜的膜通量提高明显,截留率基本不变;若处理时间过长或者处理剂浓度过大,则膜通量下降.

料液中盐对气态膜法脱氨过程的影响

系统研究了气态膜法脱氨操作过程中无机盐种类和浓度对氨传质性能的影响,并初步探讨了温度对盐效应的影响。实验结果表明,盐效应和盐溶液的黏度变化均影响氨的传质。盐对氨的盐析效果越强,氨的膜相传质系数kM越大,而盐溶液的黏度越大,氨的液相传质系数kL越小,总传质系数K的变化是kM和kL变化的综合结果。在几种常见的无机盐中,氯化钠、硫酸钠、硫酸铵对氨具有不同程度的盐析效应,可促进氨在体系中的传质;而氯化铵和氯化钙对氨具有盐溶效应,其中氯化钙的盐溶效应最为明显。温度对盐效应和体系的传质性能有显著影响,硫酸铵和氯化钙的盐效应均随着温度的升高而减弱。