A rational asymmetric hollow fiber membrane for oxygen permeation

A typical oxygen permeation hollow fiber membrane fabricated by phase inversion-based extrusion process demonstrates heterogeneous porous microstructures, in which the surface layer with relatively low porosity is used as a separation layer after sintering. It is usually not convenient to control the thickness of separation layer. And a high sintering temperature is needed to densify the separation layer, which in turn could destroy the desired porous microstructures in other portion. This paper studies a novel process to fabricate multilayer asymmetric hollow fiber membrane with a rational design using 67 vol. % Gd_0.2Ce_0.8O_2−δ−33 vol. % La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (GDC-LSCF) as a model material system. The phase inversion-based extrusion process in open literature is employed to fabricate a hollow fiber substrate featuring radially well-aligned microchannels open at the inner surface. Built upon the hollow fiber substrate, a thin dense separation layer and porous surface catalyst layer at shell side are then fabricated through dip-coating and sintering process alternatively. The oxygen permeation flux of the fabricated hollow fiber membrane reaches 2.68 mL/cm²/min at 900°C under Ar/air gradient, the highest performance of the membranes with GDC-LSCF material system in open literature. The innovative fabrication process is able to readily control the thickness of functional layers while decreasing sintering temperatures.     

新型中空纤维膜接触器用于乙醇/水体系分离的探索

引言 醇/水体系分离一直是化工生产中的重要环节,高效的醇/水分离技术能够使醇的产量大大提高,满足日益增长的工业生产需求.传统的分离方法如精馏、萃取等已经相当成熟,但是这些方法在工业生产过程中能耗巨大,越来越受到面临能源资源匮乏的当代社会的关注和制约.在此背景下,面向高效、节能的新型膜接触分离器应运而生,如Alan等[1]指出,工业化或半工业化的过程已经包括膜吸收、膜萃取以及渗透蒸馏等多个耦合分离单元[2-6].     

Latent skin in asymmetric loeb-type hollow fiber membrane

A computer simulation model for the latent skin growth inside a hollow fiber polymeric membrane Is developed. The evaporation step is studied using a solvent evaporation Law and a concentration-dependent diffusion coefficient, both derived from data. The solvent concentration profiles inside the fiber are obtained as a function of the evaporation time for different sets of the parameters governing the internal diffusion and the surface evaporation of the solvent. The computer model enables estimation of the role of the parameters in the growth of the asymmetric latent skin.     

Factorial design in optimization of the separation of uranium from yellowcake across a hollow fiber supported liquid membrane,with mass transport modeling

The extraction and stripping of uranium(VI) from other impurity elements in yellowcake was performed simultaneously in one stage by a hollow fiber supported liquid membrane. Uranium ions were selectively extracted from yellowcake using TBP as the extractant, while thorium and some rare earth elements were rejected in the raffinate. The optimization method was carried out using 3² factorial design. The concentration of nitric acid in the feed solution and the concentration of TBP in the liquid membrane were regarded as factors in the optimization. A mass transport model focusing on the boundary layer of the extraction side was also applied. The model can predict the concentration of uranium in the feed tank at different times. The validity of the developed model was statistically evaluated through a comparison with experimental data, and good agreement was obtained.     

中空纤维式渗透汽化膜内流动的CFD模拟

采用计算流体动力学(CFD)数值模拟软件研究了入口速度和管径对中空纤维式渗透汽化膜内流动特征及分离性能的影响.结果表明,膜通道内压降和壁面剪切应力与入口速度呈正相关,与管径呈反相关;分离性能随着入口速度的增大,呈现先增大后减小的趋势;管径越小,分离性能越高.     

Simulation of gas separation using partial element stage cut modeling of hollow fiber membrane modules

A mathematical model is developed to simulate a gas separation process using a hollow fiber membrane module. In particular, a new numerical technique is introduced based on flash calculation. Such analysis allows identifying the required membrane properties needed to reach module performance of interest. This model is validated for six different gas separation cases taken from literature. Then, the validated model is used to investigate the effect of O₂ and N₂ permeances on O₂ recovery and O₂ mole fraction in the permeate stream. A realistic two‐stage air enrichment process is also proposed for O₂ production using an industrial module with different fibers numbers. Moreover, this model is used to simulate a natural gas purification process using a single unit to determine the required membrane separation area and CH₄ loss. Finally, a two‐stage process is proposed to equally enhance CH₄ retentate mole fraction and decrease CH₄ loss. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1766–1777, 2018     

中空纤维膜分离烟气CO_2工艺模拟优化

为了分离燃煤电厂烟气中的二氧化碳,基于Matlab软件的Simulink组件对三级中空纤维膜装置进行模拟优化。建立了中空纤维膜的数学模型,使用Matlab软件编程;并针对经过预处理后CO_2体积分数15%,气量50 000 m~3/h的电厂烟气,在Simulink组件中模拟了分离工艺流程。膜材料采用经过氟化改性的聚酰亚胺6FDA/TAPA[六氟二酐/三(4-氨基苯基)胺)]。研究结果表明:随着膜面积和压力的增加,产品气中CO_2体积分数与CO_2回收率呈反比关系;所需的一、二、三级膜面积分别为42 000,50 000,5 200 m~2,需要的压缩机压力为一级0.7 MPa、二级0.65 MPa、三级1.5 Ma。最终得到的CO_2产品气流量为6 648.81 m~3/h,CO_2纯度86.88%,CO_2回收率77.02%,在满足分离要求的同时降低了碳排放。     

Modeling study of oxygen permeation through an electronically short‐circuited YSZ‐based asymmetric hollow fiber membrane

Here, oxygen fluxes through an electronically short‐circuited asymmetric Ag‐YSZ|YSZ|LSM‐YSZ hollow fiber prepared via a combined spinning and sintering route were tested and correlated to an explicit oxygen permeation model. The average oxygen permeation through such asymmetric hollow fiber with a 27 μm‐thick YSZ dense layer reached 0.52 mL (STP) cm^?2 min^?1 at 1173 K. From the model results, we can obtain the characteristic thickness, the effects of the temperature, and the effect of He sweep gas flow rate to the individual step contribution. The oxygen partial pressure variation in the permeate side, the local oxygen flux, and the three‐different resistance distribution along the axial direction of the asymmetric hollow fiber are theoretically studied; providing guidelines to further improve the membrane performance for oxygen separation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3491–3500, 2017     

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 generation and purification in a composite Pd hollow fiber membrane reactor: Experiments and modeling

“Pd nanopore” composite membranes are a novel class of H₂ permselective membranes in which a thin layer of Pd is grown within the pores of a supported nanoporous layer. In this work, Pd nanopore membranes and conventional Pd top-layer membranes were used in the generation of high-purity H₂ from the catalytic decomposition of anhydrous NH₃. An effective 4 μm thick Pd nanopore membrane and 13 μm thick Pd top-layer membrane were synthesized on 2 mm O.D. α-Al₂O₃ hollow fibers. The permeation features of the membranes were determined and the membranes were then employed in a single fiber packed-bed membrane reactor in which Ni-catalyzed NH₃ decomposition served as the test reaction, with conditions spanning a range of conditions (500–600 °C; 3–5 bar total retentate pressure; 60–1200 scc/h g cat space velocity). The NH₃ conversions in both the PBMRs were approximately 10% higher than in a packed-bed reactor (PBR) under similar conditions. The increase in conversion with the PBMR was attributed to the removal of H₂, which has an inhibitory effect on the forward kinetics of the reaction as per the Temkin-Pyzhev type rate mechanism. Reactor productivities in the range of 2 mol/s m³ (at 85% H₂ utilization) to 7 mol/s m³ (at 50% H₂ utilization) were obtained. The permeate stream purity exceeded 99.2% H₂. A two-dimensional pseudo-homogeneous model was successfully used to simulate the experimental results and to interpret the findings. Permeation and kinetic parameters were estimated in permeation and PBR experiments, respectively. Without any data fitting the PBMR model predictions demonstrated very good agreement with experimental trends. Together with an analysis of the characteristic times, the model determined that transverse transport of hydrogen in the catalyst bed limited PBMR performance. The model was used to determine the rate limiting step and to suggest ways in which the reactor productivities could be further improved.     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

Preparation and performance evaluation of composite hollow fiber membrane for SO2 separation

Emission of sulfur dioxide (SO₂) from coal power plants has to be controlled and minimized to reduce environmental risk. This study aimed to investigate the hollow fiber composite membrane was used for the removal of SO₂ from a SO₂/CO₂/N₂ mixed gas. Moreover, for the improvement of SO₂ removal efficiency, the polyetherimide (PEI) membrane was coated with poly(vinyl chloride)‐graft‐poly(oxyethylene methacrylate) (PVC‐g‐POEM). The PVC‐g‐POEM/PEI composite hollow fiber membrane was extensively characterized by various techniques including scanning electron microscopy, Fourier transform infrared spectroscopy, and atomic force microscopy. Experiments with permeation of SO₂, CO₂, N₂, and a ternary gas mixture were carried out to observe membrane behavior in response to different operating conditions. As a result, permeance of SO₂ was 105–2705 GPU and selectivity of SO₂/CO₂ was 3.9–175.6. From the mixed gas separation experiment, the maximum SO₂ removal efficiency reached up to 84.5%. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2298–2306, 2014     

Modeling and control of CO2 separation process with hollow fiber membrane modules

A multi-stage model is developed for CO₂ separation by hollow-fiber membrane. The model permits rapid solution of the governing differential mass and pressure distribution in hollow-fiber gas separation modules using a computational scheme that does not rely on commercial software and conventional numerical methods such as shooting techniques. For 1-stage, 2-stage and 3-stage configurations the changes of required separation areas according to stage cuts are computed. A simple model predictive control technique is employed to provide optimal operation conditions based on the proposed model. Values of stage cuts can easily be identified for various desired mole fractions and recovery rates. From the results of numerical simulations, we can see that the proposed model can be effectively used in the control of gas separation process by hollow-fiber membrane modules.     

Design of metallic nickel hollow fiber membrane modules for pure hydrogen separation

Cost‐effective and robust nickel (Ni) membrane for H₂ separation is a promising technology to upgrade the conventional H₂ industries with improved economics and environmental benignity. In this work, Ni hollow fibers (HFs) with one closed end were fabricated and assembled into a membrane module for pure H₂ separation by applying vacuum to the permeate side. The separation behavior of the HF module was investigated both experimentally and theoretically. Results indicate that H₂ recovery can be improved significantly by changing the operation conditions (temperature or feed pressure). Ni HF is a promising membrane geometry, but the negative effect of pressure drop when H₂ passes through the lumen cannot be ignored. Under the vacuum operation mode, there is little difference in term of H₂ recovery efficiency whether the feed gas flow is controlled in countercurrent or recurrent operation. This work provides important insight to the development of superior membrane H₂ separation system. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3662–3670, 2018     

One-through selective separation of copper,chromium and zinc ions by hollow fiber supported liquid membrane

The separation of a mixture of Cu(II), Cr(VI) and Zn(II) simultaneously from a sulfate media using two consecutive hollow fiber microporous liquid membrane extraction systems has been studied. The experiments were made in the one-through mode. LIX84-I and Aliquat336 were used as carrier extractants for copper and chromium in the first and second hollow fiber modules, respectively. Pure copper and pure chromium ions are extracted and stripped from first and second hollow fiber modules, respectively, but zinc ions cannot be extracted by both extractants due to pH conditions used in this study and remain in the raffinate. Results indicate that the percentage of extraction is highly dependent on pH of the feed solution and the pH value is 2.5 for the maximum extraction. The percentage of extraction of copper and chromium ions is enhanced when the concentration of LIX84-I and Aliquat336 is increased of which both maximum value is 0.5 M, and these results also occur in stripping phase. The influence of sulfuric acid and sodium hydroxide concentration in strip solution of each column was examined, and it was found that the percentage of extraction and stripping is further increased due to the difference of driving force. The maximum percentage of extraction for copper is 33% and 92% for chromium. The experimental results indicated the feasibility of separation and recovery of these metals from the dilute solution by using membrane technology     

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。     

旋流强化中空纤维膜组件结构优化及壳程流动研究

提出并优化了一种旋转流强化的膜组件水力学模型。Box-Behnken方法用于进口直径、进口长度、膜壳高度、进/出口端管长度、球突结构直径,进出口倾斜角度的多参数的实验设计,获得了响应变量最优的膜组件设计方案。通过雷诺应力RSM湍流模型与基于Euler-Lagrange算法的离散相DPM模型的耦合计算,模拟研究了三维模型内液固两相流的颗粒停留时间分布、流体力学特征。模拟结果显示,旋流强化的膜组件壳程的速度分布更加均匀,膜面剪切应力高;湍流耗散率、涡量分布不同于传统膜组件。实验结果证实,优化后的膜组件具有高产水量、低压力降,膜污染速率低的特点。     

Gas separation by permeation Part I. Calculation methods and parametric analysis

Calculation methods for single- and multi-stage permeation of a multi-component mixture are presented. The use of the local permeate concentration in the formulation results in a relatively simple form of solution for the binary system in the cross-flow pattern. A parametric analysis of the permeation cascade is given. For a given permeability of the more permeable component, there exists a membrane selectivity which gives rise to a minimum membrane area requirement in the cascade. It is shown that the compression power requirement is dependent only on the operating pressure ratios, irrespective of actual pressure levels in each stage. A study on the effect of interstage mixing loss shows that the ideal cascade (with no interstage mixing loss) is not necessarily always the thermodynamically most efficient one; some non-ideal cascades may have higher efficiencies due to more effective permeation steps. Examples given relate to He/CH₄ and O₂/N₂ separations.     

Gas absorption of carbon dioxide in a hollow fiber contained liquid membrane absorber

Experiments on the absorption of CO₂ into a hollow fiber contained liquid membrane absorber were performed. The feed gas was a mixture of CO₂ and N₂, absorbent liquid was 2-amino-2-methyl-l-propanol and the hollow fiber was a microporous hydrophobic polytetrafluoroethylene membrane. Outlet concentration of CO₂ from the absorber decreased as absorbent concentration increased, gas flow rate increased and were held constant for speed of agitation, but had a maximum value in the range of inlet concentration of CO₂ from 5 to 40 mole%. The reaction rate constant obtained for CO₂-amine system was 231 I/mol · s at 25 °C using a flat stirred vessel, and the membrane-side-mass-transfer coefficient was 1.217 × 10⁻⁵ mol/cm² · s · atm in CO2/N2-amine system. A diffusion model based on mass transfer with fast-reaction was proposed to predict the performance of the absorber.     

聚丙烯中空纤维膜组件分离烟气中的CO2

膜吸收法在大型工业燃煤电厂二氧化碳（CO2）捕集方面具有很好的应用前景,但烟气组分对该技术效果影响还有待进一步研究。本文以单乙醇胺（MEA）为吸收剂,开展了疏水性聚丙烯（PP）中空纤维膜组件分离模拟烟气中的CO2的实验研究,考察了吸收操作条件以及燃煤烟气中水汽和SO2对膜组件吸收效率的影响。结果表明,试验的最佳液气比为24 L/m3;MEA的浓度为0.6 mol/L;膜组件进口的温度变化对吸收效率基本没有影响;CO2的浓度在10%～20%内变动对吸收效率影响不大。与CO2相比,SO2会优先发生吸收作用,而水汽则会吸附在聚丙烯中空纤维膜组件的孔壁上,产生毛细管凝聚现象,阻塞CO2的渗透吸收。