相转化法制备氧化钇稳定氧化锆中空纤维陶瓷膜

采用相转化和烧结相结合的方法制备了氧化钇稳定氧化锆(YSZ)中空纤维陶瓷膜，研究了铸膜液中YSZ粉末含量和烧结温度对中空纤维陶瓷膜的微观结构和性能的影响。结果表明，YSZ中空纤维陶瓷膜的不对称结构包含指状结构和海绵状结构，YSZ含量会影响两种结构的比例，烧结则会引起微观结构的致密化。在铸膜液配比为m(YSZ):m(PSF):m(NMP)=5.0:1:4，烧结温度为1200 ℃的条件下制备出性能良好的中空纤维陶瓷膜，其纯水通量为2.33 m3/(m2·h·MPa)，抗弯强度为134.5 MPa。     

Fundamental understanding of the effect of air‐gap distance on the fabrication of hollow fiber membranes

The objectives of this work are, fundamentally, to understand hollow fiber membrane formation from an engineering aspect, to develop the governing equations to describe the velocity profile of nascent hollow fiber during formation in the air gap region, and to predict fiber dimension as a function of air‐gap distance. We have derived the basic equations to relate the velocity profile of a nascent hollow fiber in the air‐gap region as a function of gravity, mass transfer, surface tension, drag forces, spinning stress, and rheological parameters of spinning solutions. Two simplified equations were also derived to predict the inner and outer diameters of hollow fibers. To prove our hypotheses, hollow fiber membranes were spun from 20 : 80 polybezimidazole/polyetherimide dopes with 25.6 wt % solid in N,N‐dimethylacetamide using water as the external and internal coagulants. We found that inner and outer diameters of as‐spun fibers are in agreement with our prediction. The effects of air‐gap distance or spin‐line stress on nascent fiber morphology, gas performance, and mechanical and thermal properties can be qualitatively explained by our mathematical equations. In short, the spin‐line stresses have positive or negative effects on membrane formation and separation performance. A high elongational stress may pull molecular chains or phase‐separated domains apart in the early stage of phase separation and create porosity, whereas a medium stress may induce molecular orientation and reduce membrane porosity or free volume. Scanning electron microscopic photographs, coefficient of thermal expansion, and gas selectivity data confirm these conclusions. T_g of dry‐jet wet‐spun fibers is lower than that of wet‐spun fibers, and T_g decreases with an increase in air‐gap distance possibly because of the reduction in free volume induced by gravity and elongational stress. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 379–395, 1999     

Three‐dimensional simulation of the time‐dependent fluid flow and fouling behavior in an industrial hollow fiber membrane module

A novel three‐dimensional CFD model has been developed on the basis of fluid flow in the shell and lumen sides, and permeation and fouling behavior in the porous membrane zone. The simulated 25‐min dead‐end outside‐in filtration process showed that the energy consumed by the inlet manifold decreases during the constant pressure filtration. The velocity and pressure distributions in the module change with time. Flux distribution both in the axial and radial directions becomes increasingly more uniform, so does the cake distribution. Flux distribution and cake distribution inter‐adjust each other in different modes. A correlation equation has been developed to describe the relationship between the volumetric flow rate and accumulated water production. The correlation equation with simple experiment enables the dynamic evolution of energy consumed by shell inlet manifold to be presented, which can be the criterion of how well the shell inlet manifold or module has been designed. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2655–2669, 2018     

PVDF-ZrO2复合中空纤维膜在乳化油废水中的应用

针对普通聚偏二氟乙烯(PVDF)中空纤维膜具有疏水性强、易污染的应用缺陷,在制备纳米粒子掺杂改性的PDVF-ZrO2复合中空纤维膜前期工作基础上,表征了其微观结构,并考察了其在油水体系中的分离效果。微观结构检测表明,随着ZrO2含量的增大,复合膜的断面微观结构完成由指状大孔向海绵状结构的转化。PDVF-ZrO2复合膜的接触角和牛血清蛋白(BSA)吸附实验结果显示其亲水性及抗污染性能均得到了提高。进一步考察了PDVF-ZrO2复合中空纤维渗透分离性能,ZrO2纳米粒子质量分数为0.3%时,显示了最佳的渗透性能。在乳化油废水处理过程中,在油质量浓度为1 g/L,操作压力为0.1MPa、搅拌强度为20 r/min条件下,通量为105 L/(m2.h),TOC去除率为95.4%,表明具有较好的废水处理效果。     

A robust mixed‐conducting multichannel hollow fiber membrane reactor

To accelerate the commercial application of mixed‐conducting membrane reactor for catalytic reaction processes, a robust mixed‐conducting multichannel hollow fiber (MCMHF) membrane reactor was constructed and characterized in this work. The MCMHF membrane based on reduction‐tolerant and CO₂‐stable SrFe_0.8Nb_0.2O_3‐δ (SFN) oxide not only possesses a good mechanical strength but also has a high oxygen permeation flux under air/He gradient, which is about four times that of SFN disk membrane. When partial oxidation of methane (POM) was performed in the MCMHF membrane reactor, excellent reaction performance (oxygen flux of 19.2 mL min^?1 cm^?2, hydrogen production rate of 54.7 mL min^?1 cm^?2, methane conversion of 94.6% and the CO selectivity of 99%) was achieved at 1173 K. And also, the MCMHF membrane reactor for POM reaction was operated stably for 120 h without obvious degradation of reaction performance. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2592–2599, 2015     

中空纤维膜组件壳程流动的数值模拟

利用随机顺序添加算法(RSA)建立了中空纤维膜组件壳程三维几何模型,研究了膜组件壳程复杂结构条件下的流体力学特征,进行了组件壳程流动的数值模拟。通过与实验数据及现有经验关联式的比较表明,在低Reynolds数下,基于上述几何模型的数值模拟可较好地预测膜组件的传质特性,能够替代经验关联式,为具有特定几何结构的膜组件和膜过程设计提供依据。模拟结果表明,膜丝轴向的非平行分布导致的径向流动能够消除局部沟流和死区带来的影响,合理地安排膜丝沿组件轴向的排布方式是提高组件分离性能的潜在手段之一。     

Pushing the limits of high performance dual‐layer hollow fiber fabricated via I2PS process in dehydration of ethanol

The immiscibility induced phase separation (I²PS) process was introduced as a novel method to fabricate hollow fibers with exceptionally high water permeance and reasonably high water/ethanol selectivity in dehydration of ethanol by pervaporation. As a continuation of the previous work, this study discloses the mechanisms to enhance the performance of hollow fibers spun via I²PS by elucidating the material selection at the inner‐layer. Moreover, it revealed the methods to reduce mass‐transport resistance by enhancing surface porosity for both inner and outer surfaces to further improve the permeation flux of the membranes. The continuous performance test demonstrates that the fibers spun from the I²PS possess a stable dehydration performance throughout the monitored period of 300 h. A comparison with pervaporation membranes in the literatures verifies the superiority of the membranes spun via I²PS process with the highest water permeation flux of 9.5 kg/m² h and the permeate water purity of 95.8 wt % at 80°C. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3006–3018, 2013     

中空纤维渗透汽化膜分离研究现状与展望

本文综述了中空纤维渗透汽化膜分离的研究进展,包括中空纤维支撑膜的制备、复合膜的制备方法、中空纤维渗透汽化膜的工业应用和中空纤维渗透汽化膜传质特性等几个方面,对这个方面所存在的问题以及今后发展方向进行了展望.     

Hydrogen separation at elevated temperatures using metallic nickel hollow fiber membranes

Nickel is a cheaper metallic material compared to palladium membranes for H₂ separation. In this work, metallic Ni hollow fiber membranes were fabricated by a combined phase inversion and atmospheric sintering method. The morphology and membrane thickness of the hollow fibers was tuned by varying the spinning parameters like bore liquid flow rate and air gap distance. H₂ permeation through the Ni hollow fibers with N₂ as the sweep gas was measured under various operating conditions. A rigorous model considering temperature profiles was developed to fit the experimental data. The results show that the hydrogen permeation flux can be well described by using the Sieverts’ equation, implying that the membrane bulk diffusion is still the rate‐limiting step. The hydrogen separation rate in the Ni hollow fiber module can be improved by 4–8% when switching the co‐current flow to the countercurrent flow operation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3026–3034, 2017     

Hollow fiber nanofiltration membranes: A comparative review of interfacial polymerization and phase inversion fabrication methods

Membrane-based separation is now established as one of staple technologies used in water treatment and reuse applications. Nanofiltration, in particular, can be a cost-effective solution for removing large ions and low-molecular-weight compounds from water. Nanofiltration membranes have been manufactured mostly as flat sheets and used in spiral wound modules. Hollow fiber geometry, however, offers several advantages over flat sheet and other configurations. This paper overviews recent developments in the design of hollow fiber nanofiltration membranes and provides a comparative analysis of two main methods of their fabrication: interfacial polymerization and phase inversion.     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Effect of hypochlorite treatment on performance of hollow fiber membrane prepared from polyethersulfone/N‐methyl‐2‐pyrrolidone/tetronic 1307 solution

Polyethersulfone (PES) hollow fiber membrane was prepared by blending with nonionic surfactant Tetronic 1307 to improve its hydrophilicity. The membranes were posttreated by hypochlorite solution of 10, 100, 500, and 2000 ppm. The effect of hypochlorite treatment on the performance of PES membrane was investigated. Experimental results showed that the water permeability of treated membrane was two to three times higher than that of untreated membrane in case of blend membrane prepared from PES/N‐methyl‐2‐pyrrolidone (NMP)/Tetronic 1307 solution. On the other hand, hypochlorite treatment has no effect on water permeability of the membrane prepared from PES/NMP solution. Elemental analysis and ATR–FTIR measurement results indicated that hypochlorite treatment led to decomposition and leaching out of Tetronic 1307 component from the membrane. The change of membrane surface structure by the hypochlorite treatment was confirmed by atomic force microscopy measurement. The hypochlorite treatment brought about no significant impact on the mechanical property of the membranes. This indicated that the hypochlorite treatment of PES membrane prepared with surfactant was a useful way to improve the water permeability without the decrease of membrane strength. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and membrane performance of poly(ethylene-co-vinyl alcohol) hollow fiber membrane via thermally induced phase separation

Poly(ethylene-co-vinyl alcohol) (EVOH) hollow fiber membranes with ultrafiltration performance were prepared from EVOH/glycerol systems via thermally induced phase separation (TIPS). The diluent glycerol was used as bore liquid to make a lumen of the hollow fiber for the purpose of prevention of the diluent evaporation and the larger pores formation at the inner surface of the hollow fiber. The obtained hollow fiber membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The formation of the larger pores near the outer surface was due to the enhanced pore growth by the water penetration. Some primary factors affecting the structure and performance of the membranes such as ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed were studied extensively. The water permeability can be improved by increasing the water bath temperature and the take-up speed and by decreasing the EC. Both the pore size at the outer surface and the connectivity between the pores have to be considered together to understand the experimental result of the water permeability and the solute rejection.     

Modification of preparation method for polymer inclusion membrane (PIM) to produce hollow fiber PIM

A new preparation method for polymer inclusion membrane (PIM) was developed. The preparation method—called post‐treatment method—is very convenient to prepare a hollow fiber PIM. Using this method, a commercial cellulose triacetate (CTA) hollow fiber membrane can be easily converted into a hollow fiber PIM. Thus, a CTA hollow fiber membrane was allowed to swell in 2‐nitrophenyl‐n‐octyl ether (NPOE) in the presence of chloroform as a solvent for CTA and N,N,N′,N′‐tetraoctyl‐3‐oxapentane diamide (TODGA) as a carrier. After evaporating chloroform, a hollow fiber PIM containing NPOE and TODGA was obtained. The result of the transport experiment of cerium(III) ions using the hollow fiber PIM showed that cerium ions were effectively transported from the feed solution to the strip solution through the hollow fiber PIM, indicating that the hollow fiber PIM was successfully prepared using the post‐treatment method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4372–4377, 2006     

液膜技术原理及中空纤维更新液膜

液膜技术可以实现萃取和反萃的耦合,具有独特的分离优势。因为具有非平衡传质的特性,液膜技术传质推动力大,萃取相用量很少。回顾了液膜技术的原理,指出液膜技术的关键在于形成一层厚度薄且相当稳定的液膜相。分析介绍了近年来发展起来的各种液膜技术的优缺点,提出了一种中空纤维更新液膜技术,其体积传质系数比传统萃取塔的大530倍。     

中空纤维膜外压全量过滤动态过程的数值模拟

建立了中空纤维膜外压式全量过滤的CFD模型,模拟膜丝长度、直径、渗透系数、装填密度、污染指数以及跨膜压差不同条件,得到通量分布和产水量的动态演变过程。研究结果表明：通量分布会随着过滤的进行而逐渐变得均匀,这种通量分布的自我调节作用在膜丝较长、较细,渗透性较好,装填密度较高,污染指数较高以及跨膜压差较高时更为明显;产水流量的倒数与累积产水量呈线性关系,但由于通量分布不均匀并且均匀性演变,这种线性关系区别于传统滤饼过滤模型;通过数据拟合得到了适用于中空纤维外压式全量操作的滤饼过滤关联式,可用于预测组件的性能和指导组件的设计。     

Spray Characteristics of Two‐phase Feed Nozzles

The present study focuses on understanding the spray characteristics of a turbulent gas‐liquid jet (Re_liq = 24,000). Air and water are used as the test fluids. The angles of injection of the two phases upstream of the nozzle are varied (θ = 20°, 45° and 90°) and the effect of carrier gas on the droplet characteristics is are also investigated. The droplet size and velocity are non‐intrusively measured using a Phase‐Doppler Particle Analyzer (PDPA). In some respects, the characteristics of the present two‐phase jet are similar to those noticed in previous studies, while revealing some important differences. The centreline mean droplet velocities (15 ～ 20 m/s) increase in the initial region of the jet, attain a maximum and then decrease at larger distances from the nozzle exit. Most of the entrainment occurs at the tip of the nozzle and the jet expansion rate decreases significantly at distances where the spray velocity profiles become self‐similar. A Lorentz‐type fit has been used to model the normalized radial velocity profiles. The results indicate that the test configuration with θ = 45° may be beneficial for the scenario discussed.     

中空纤维渗透汽化复合膜及组件研究进展

中空纤维渗透汽化膜组件具有器件小型化及成本较低等方面的优势,其工业应用潜力巨大。本文介绍了中空纤维渗透汽化复合膜及组件的研究进展,阐述了膜材料、成膜方法以及组件结构参数等对组件渗透汽化性能的影响,并对中空纤维渗透汽化膜组件的中试研究进行了总结。通过组件放大及中试研究发现,中空纤维渗透汽化膜组件的装填密度、长度以及抽吸方式均会影响其下游侧的真空度,从而影响其渗透汽化性能。膜材料的分子设计、组件的结构参数优化以及耐溶剂耐高温封装将是中空纤维渗透汽化膜组件未来工业放大过程中的关键环节。     

New chlorine‐resistant polyamide reverse osmosis membrane with hollow fiber configuration

New asymmetric hollow fiber reverse osmosis (RO) membrane was developed from a new chlorine‐resistant copolyamide [4T‐PIP(30)] with a piperazine moiety by a conventional phase‐separation method. The new 4T‐PIP(30) hollow fiber membrane has the same low‐pressure RO performance as cellulose triacetate hollow fiber membrane (FR = 205 L/m² day, Rj = 99.6%) and superior chlorine resistance as well as pH resistance to conventional aramid RO membranes. Structural analysis and viscoelastic study revealed that the new hollow fiber consisted of a top skin, dense layer, and microporous layer, and that it began to decrease its elasticity at 80°C in water, which is possibly related to its good and stable RO performance around room temperature. Several kinds of RO modules were made from the new hollow fiber membranes, for which RO performances were stable for 2 years in chlorinated feed water desalination (the free residual chlorine ranged from 0.l to 1.1 mg/L). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 517–527, 2001     

The removal of toxic heavy metal cations by polysulfonebenzylthiourea reactive hollow fiber ultrafiltration membranes

The hollow fiber asymmetric matrix membranes were prepared with phase inversion by utilization of the chloromethyl polysulfone/polyethylene glycol/DMAC casting solution and chloromethyl polysulfone as membrane materials. The effects of composition of spinning casting solution and process parameters of dry–wet spinning on the structure of hollow fiber matrix membrane were investigated. Through the reaction between matrix membrane and thiourea, the highly qualified polysulfonebenzylthiourea reactive hollow fiber ultrafiltration membranes were able to afford. The adsorption isotherms of the polysulfonebenzylthiourea hollow fiber membrane for Cd²⁺ and Zn²⁺ were determined and the effects of mobile phase conditions and the operating parameters on removal performance of the polysulfonebenzylthiourea hollow fiber membrane for Cd²⁺ and Zn²⁺ were also investigated. The experimental results showed that adsorption isotherms of Cd²⁺ and Zn²⁺ could be described by the Langmuir isotherm, the polysulfonebenzylthiourea hollow fiber membrane could be operated at high feed flow rate, and a large‐scale removal of Cd²⁺ and Zn²⁺ could be realized. According to required recovery of Cd²⁺ and Zn²⁺ and the saturation degree of polysulfonebenzylthiourea hollow fiber membrane, the optimum loading amount of Cd²⁺ and Zn²⁺ should be selected in the actual removal of Cd²⁺ and Zn²⁺. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009