新型中空纤维空气隙式膜蒸馏用于海水淡化

利用自制的添加隔热管状隔网并呈螺旋缠绕结构编排的中空纤维膜组件进行了空气隙式膜蒸馏(AGMD)海水淡化过程性能研究, 实验以模拟标准海水(质量分数3.5%, 总溶解性固体含量35000 mg·L^-1)为热料液进水, 考察了热料液进水温度、热料液流量、冷凝液进水温度和冷凝液流量对膜通量、造水比和热效率的影响。结果表明, 随着热料液进水温度增加, 膜通量、造水比和热效率均增加;冷凝液进水温度增加, 膜通量下降而造水比和热效率增加;热料液流量增加, 膜通量上升而造水比和热效率明显下降;冷凝液进水流量对膜蒸馏过程性能影响较小。实验过程中产水TDS始终保持在3.0 mg·L^-1以下, 相应的离子去除率高于99.99%, 膜通量、造水比和热效率最高可分别达5.87 L·m^-2·h^-1、5.37和0.943。研究表明, 引入清洁能源取代传统电加热驱动热源将进一步突出膜蒸馏技术的实际应用潜力。     

Study on a new air-gap membrane distillation module for desalination

A new air-gap membrane distillation (AGMD) module for desalination with internal latent-heat-recovery which consisted of parallel hollow fiber membranes and heat exchange hollow fibers was successfully developed. The influences of feed flow rate, feed temperature and feed initial concentration on AGMD process were investigated. The vapor pressure polarization coefficient (η) was introduced to measure the reduction in the effective driving force for mass transfer with regard to the driving force imposed. Among all AGMD experiments, the maximum water vapor permeate flux (J_D) of 5.30 kg/m² h and the gained output ratio (GOR) of 5.70 were obtained. A theoretical model based on the mass and energy balances of the hot feed side was established to calculate the temperature and the local water vapor permeate flux distributions along the hollow fiber membrane, which showed that the temperature drop and local water vapor permeate flux drop were much larger at the upper part than those at the lower part of the membrane module in the hot feed side.     

中空纤维空气隙式膜蒸馏海水淡化过程的性能模拟与优化

利用响应曲面法(RSM),以模拟标准海水(质量分数3.5%)为进水对中空纤维空气隙式膜蒸馏(AGMD-HF)海水淡化过程的影响因子和膜通量指标进行了模拟优化。通过面向中心复合设计法(CCD)实现了基于热料液进水温度、冷凝液进水温度和料液流量的实验优化设计,并建立了响应值与影响因子之间的二次多项式回归模型。方差分析(ANOVA)、RSM分析及实验响应值与预测值的对比验证了该模型对影响因子和膜通量模拟优化的可信度。进一步地,通过期望函数的引入确定了各影响因子最佳水平,并利用太阳能加热驱动过程实验进行验证。结果表明,ANOVA的决定系数R²达到0.986,p值则低于0.0001;实验膜通量与预测值平均误差仅为6.95%,产水电导率始终保持在10 μS·cm^-1以下,脱盐率稳定在99.99%以上;最佳影响因子水平分别为83.5℃、13.2℃和60.2 L·h^-1,在此条件下太阳能加热驱动过程膜通量达到6.47 L·m^-2·h^-1。该实验不仅为潜在可行的规模放大过程提供了可参照的操作参数,而且表明将太阳能引入AGMD-HF海水淡化过程具有很强的实际应用潜力。     

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     

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     

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     

往复旋转中空纤维膜处理脱脂奶水溶液

采用一种往复旋转中空纤维膜超滤装置处理脱脂奶水溶液,考察了该膜过滤装置的结构参数、膜组件旋转参数以及料液的特征参数等对膜渗透通量衰减的影响。结果表明,旋转角速度越大,膜丝距中空轴轴心越远,往复旋转中空纤维膜的剪切强化作用越好;往复旋转周期的优化则需考虑如何使料液流场流速与膜丝转速之间的矢量迭加在膜表面产生的速度梯度更大,单纯增大或减小旋转周期均会弱化剪切强化的效果。在同样操作参数下,往复旋转方式比死端过滤及单向旋转方式的膜过滤更利于延缓膜通量衰减。     

Two‐dimensional simulation of hollow fiber membrane fabricated by phase inversion method

In the steady fabricating process, two‐dimensional hollow fiber membrane near the spinneret was numerically simulated using the finite element method (FEM). The unknown positions of free surface and moving interface were calculated simultaneously by the velocity and pressure fields. The effects of seven relevant parameters, i.e., inertia term, gravity term, dope flow rate, bore flow rate, dope viscosity, tensile force, end velocity and non‐Newtonian on the velocity and diameter profile were studied. On the basis of the simulated results, the inertia term in hollow fiber‐spinning process was safely neglected in low speed, while the effect of gravity was not be neglected. Besides, the outer diameter of the fibers increased with an increase of dope flow rate and bore flow rate; Large tensile force or large end velocity could cause large deformation in the air gap; larger viscous dope solution tended to make less deformation in the air gap. It was found that an increase of the dope flow rate at small dope flow rate resulted in an increase of the inner diameter, while at large dope flow rate, it decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2067–2074, 2006     

中空纤维膜管束液体除湿再生过程中的热湿耦合传递

研究了中空纤维膜管束液体除湿再生过程中的热湿耦合传递特性。选择了两根膜纤维管及其管内部溶液流和管间空气流作为研究对象,建立了控制流体流动与传热传质过程的偏微分方程,并采用有限容积离散方法和贴体坐标转换方法进行求解,获得了计算单元内的阻力系数、Nusselt数和Sherwood数,分析了耦合边界条件下的Nusselt数和Sherwood数与相应等壁温和等热流密度边界条件下的相应准则数之间的差异。这些研究结果可以为用于液体除湿再生过程的中空纤维膜管束构成的膜接触器的结构设计提供理论基础。     

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     

Filtration of biomass with laboratory‐scale submerged hollow fibre modules – effect of operating conditions and module configuration

The filtration behaviour of submerged hollow fibres, the effect of gas flow rate, feed concentration, module configuration and fibre diameter have been assessed by filtration of yeast suspensions. The fouling behaviour of the submerged hollow fibre was affected by the average imposed flux, flux distribution, and local critical flux. The results suggest that stable performance is obtained when the averaged imposed flux (J_mi) is lower than the critical flux (J_cr) although an initial deposition may occur due to the high local initial flux. In addition, the module configuration had a critical influence on filtration performance. Comparison between tight and loose modules indicated that the loose module [1.0 > (fixed ends distance/fibre length) > 0.95] was significantly better than the tight bundle at high feed concentration or low gas flow rates due to reduced inter‐fibre clogging. The study also showed that the smaller fibre was better than the larger fibre for filtration with bubbling with the submerged hollow fibre system. © 2002 Society of Chemical Industry     

A CO2‐stable hollow‐fiber membrane with high hydrogen permeation flux

A Mo‐substituted lanthanum tungstate mixed proton‐electron conductor, La_5.5W_0.6Mo_0.4O_11.25?δ (LWM04), was synthesized using solid state reactions. Dense U‐shaped LWM04 hollow‐fiber membranes were successfully prepared using wet‐spinning phase‐inversion and sintering. The stability of LWM04 in a CO₂‐containing atmosphere and the permeation of hydrogen through the LWM04 hollow‐fiber membrane were investigated in detail. A high hydrogen permeation flux of 1.36 mL/min cm² was obtained for the U‐shaped LWM04 hollow‐fiber membranes at 975°C when a mixture of 80% H₂?20% He was used as the feed gas and the sweep side was humidified. Moreover, the hydrogen permeation flux did not significantly decrease over 70 h of operation when fed with a mixture containing 25% CO₂, 50% H₂, and 25% He, indicating that the LWM04 hollow‐fiber membrane has good stability under a CO₂‐containing atmosphere. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1997–2007, 2015     

Effect of air gap on gas permeance/selectivity performance of BTDA‐TDI/MDI copolyimide hollow fiber membranes

Fabrication, morphology evaluation , and permeance/selectivity properties of three asymmetric BTDA‐TDI/MDI copolyimide hollow fiber membranes (HFM s ) are reported. The asymmetric HFM s were spun using the dry/wet phase inversion process. The effect of one of the major spinning parameters, the air gap, on the permeance/selectivity properties of the produced HFM was investigated. Scanning e lectron m icroscopy was used to evaluate the morphological characteristics and the macroscopic structure of the developed HFM. The permeance values of He, H₂, CH₄, CO₂, O₂, and N₂ gases were measured by the variable pressure method at different feed pressures and temperatures and the permselectivity coefficients were calculated. The higher selectivity values were evaluated for the Μ1 membrane and were found to be 49.33, 2.99, 5.13, 5.57 , and 9.61 for H₂/CH₄, O₂/N₂, CO₂/CH₄, CO₂/N₂ , and H₂/CO₂ gas mixtures , respectively. The selectivity experiments of H₂/CH₄, CO₂/CH₄ , and O₂/N₂ mixtures were performed at 25 ° C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4490–4499, 2013     

Effect of membrane pore size on the pH‐sensitivity of polyethersulfone hollow fiber ultrafiltration membrane

In our recent study, pH‐sensitive polyethersulfone (PES) hollow fiber membranes were prepared by blending poly (acrylonitrile‐co‐acrylic acid) (PANAA), and the electroviscous effect had great effect on the water flux change. While the question remains: is the water flux change caused by the electroviscous effect for all the membranes with different pore sizes? Herein, pH‐sensitive hollow fiber membranes with different pore sizes were prepared. The pore size and the theoretic water flux were calculated through the ultrafiltration of polyethylene glycol (PEG) solution. Comparing the calculated fluxes and the experimental ones, we found that the water flux change was mainly caused by the pore size change at the pH value larger than pKa, while that was caused by both the pore size change and the electroviscous effect when pH value was smaller than the pKa, and the pore size change was caused by the ionization of the ? COOH in the copolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Highly scalable ZIF‐based mixed‐matrix hollow fiber membranes for advanced hydrocarbon separations

ZIF‐8/6FDA‐DAM, a proven mixed‐matrix material that demonstrated remarkably enhanced C₃H₆/C₃H₈ selectivity in dense film geometry, was extended to scalable hollow fiber geometry in the current work. We successfully formed dual‐layer ZIF‐8/6FDA‐DAM mixed‐matrix hollow fiber membranes with ZIF‐8 nanoparticle loading up to 30 wt % using the conventional dry‐jet/wet‐quench fiber spinning technique. The mixed‐matrix hollow fibers showed significantly enhanced C₃H₆/C₃H₈ selectivity that was consistent with mixed‐matrix dense films. Critical variables controlling successful formation of mixed‐matrix hollow fiber membranes with desirable morphology and attractive transport properties were discussed. Furthermore, the effects of coating materials on selectivity recovery of partially defective fibers were investigated. To our best knowledge, this is the first article reporting successful formation of high‐loading mixed‐matrix hollow fiber membranes with significantly enhanced selectivity for separation of condensable olefin/paraffin mixtures. Therefore, it represents a major step in the research area of advanced mixed‐matrix membranes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2625–2635, 2014     

Laminar flow with injection through a long dead‐end cylindrical porous tube: Application to a hollow fiber membrane

Effects of membrane length and hydraulic resistance on the steady‐state laminar flow of a fluid with injection in a dead‐end cylindrical porous tube have been investigated using the perturbation approach of the Navier‐Stokes and continuity equations. Analytic solutions of the dynamic equations, reduced to non linear differential equations, were obtained and applied to submerged, dead‐end hollow fiber membranes of large resistances and small wall Reynolds numbers. The velocity and pressure profiles were solved using the method of separation of variables as with physical properties of the membrane and fluid and the wall velocity at the dead end. The constant flux approximation was found to be valid only for a short membrane with a large hydraulic resistance. The constant permeability approximation used in this study is universal for a membrane of an arbitrary length, through which the fluid velocities and pressure increase exponentially from the dead end to the open end. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Desalination with a cascade of cross‐flow hollow fiber membrane distillation devices integrated with a heat exchanger

Cost‐efficient desalination technology was developed successfully by integrating a countercurrent cascade of the novel cross‐flow direct contact membrane distillation (DCMD) devices and solid polymeric hollow fiber‐based heat exchange devices. Simulations have been carried out for the whole DCMD cascade to project values of gained output ratio (GOR) as a function of the number of DCMD stages as well as other important factors in the cascade vis‐à‐vis the temperatures and flow rates of the incoming hot brine and cold distillate streams. The simulation results were verified with experimental results from cascades consisting of two to eight stages. The numerical simulator predicts a GOR of 12 when unequal flow rates of the incoming brine and distillate streams are used. An artificial sea water was concentrated eight times successfully when a countercurrent cascade composed of four stages of the DCMD modules and a heat exchanger was used during the DCMD process. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

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