Fabrication of highly permeable PDMS@ZIF-8/PVDF hollow fiber composite membrane in module for ethanol-water separation

The construction of high-performance MOF-based hollow fiber composite membrane (HFCM) modules is a significant, yet challenging task for the biofuel production industry. In this study, a novel approach was taken to fabricate PDMS@ZIF-8/PVDF HFCMs in modules through a facile ZIF-8 self-crystallization synthesis followed by pressure-assisted PDMS infusion for pervaporation ethanol-water separation. The as-prepared HFCMs exhibited an ultrathin separation layer (thickness, 370 ± 35 nm), which was achieved through precise regulation of the ZIF-8 membrane and defect repair by PDMS infusion. Moreover, the strategy utilized in this study resolved the defect issues arising from MOF agglomeration in conventional composite membranes. Impressively, at the optimal packing density, the prepared membrane demonstrated a remarkable ethanol flux (1.11 kg m⁻² h⁻¹) with an PSI value (26.59 kg m⁻² h⁻¹) and showed promising long-term stability for the pervaporation of 5 wt% ethanol aqueous solution at 40°C.     

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.     

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。     

介孔Al_2O_3/PVDF复合中空纤维膜的制备及其性能

为了提高PVDF中空纤维膜在处理含油废水过程中的亲水性能、抗压实性能和抗污染性能,实验以介孔Al2O3为无机添加粒子,采用溶液纺丝法制备出介孔Al2O3/PVDF复合中空纤维膜。通过扫描电子显微镜和傅里叶红外光谱观察介孔Al2O3/PVDF复合中空纤维膜的形貌和成分,结果证明介孔Al2O3成功地添加到PVDF中空纤维膜中。通过接触角,纯水和含油废水通量的测试,结果表明介孔Al2O3的添加改善了PVDF膜的亲水性能、抗压实性能和抗污染性能。     

N2优先渗透ZIF-8复合膜的制备及其CO2捕集

为了获得经济节能的烟道气CO₂回收方法,制备了一种新型的N₂优先渗透ZIF-8复合膜。以柔性聚砜(PSf)多孔膜为支撑层,采用Zn²⁺与壳聚糖的交联溶液对聚砜支撑层表面改性,使Zn²⁺固定在PSf膜表面;然后与2-甲基咪唑(Hmim)配位得到ZIF-8晶种层;最后通过界面聚合法二次生长制得ZIF-8复合膜。采用FTIR、XRD及SEM对ZIF-8复合膜的形貌结构进行表征,结果显示成功制备了致密的ZIF-8复合膜。在进料气为纯气条件下,探究了二次生长时间、Zn²⁺溶液的浓度、测试时间及测试压力对ZIF-8复合膜N₂/CO₂分离性能的影响,阐明其N₂优先渗透机理;并进一步考察了混合气分离性能。结果表明：在25℃和0.1 MPa下,最优ZIF-8复合膜的N₂渗透性为523 GPU,N₂/CO₂选择性为19;同条件下混合气的N₂渗透性和N₂/CO₂选择性分别为517 GPU和18。所制备的ZIF-8复合膜可以使N₂优先渗透,实现烟道气中高浓度N₂渗透,低浓度CO₂截留在膜的上游侧。原因主要是ZIF-8复合膜含有较多的CO₂强吸附位点,使CO₂被吸附在膜内不易从膜的下游侧脱附,渗透性小,而N₂优先渗透,这为N₂优先渗透膜的制备提供了一种新思路。     

聚醚砜中空纤维膜的制备

讨论了在二次成形聚醚砜(PES)中空纤维膜的制备中,PES浓度和不同的填充液对中空纤维膜结构和性能的影响。结果发现:随着PES浓度的增大,中空纤维膜的水通量呈下降的趋势,确定了二次成形PES中空纤维膜制备中PES最佳浓度为24%;不同填充液与溶剂之间的相互扩散速率不同,得到了具有不同结构的聚醚砜中空纤维膜。随着填充液压力的提高,纤维的内径、外径增加,壁厚减小,水通量增大,一般填充液压力为0.020MPa。     

水蒸气在中空纤维复合膜中渗透的微分阻力模型

建立了水蒸气在中空纤维复合膜中渗透的微分阻力模型,用实验验证了模型的可靠性。采用该模型估算出中空纤维膜的结构参数,研究了水蒸气在各层膜中的阻力,并以H2O/C2H2系统为例,考察了膜的结构参数对H2O/C2H2选择性的影响。     

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     

中空纤维纳滤膜与反渗透膜的研究

根据界面聚合反应成膜原理,以哌嗪(PIP)或间苯二胺(m-PD)水溶液为水相,均苯三甲酰氯(TMC)正己烷溶液为有机相,以聚砜中空纤维超滤膜为基膜,制备了一系列聚酰胺/聚砜纳滤或反渗透复合膜.研究了水相浓度、有机相浓度、界面聚合时间和温度等条件对复合膜性能的影响.结果表明:中空纤维纳滤复合膜在0.4 MPa、室温条件下,对2 g/L MgSO_4水溶液的通量可达36.64 L/(m~2·h),截留率为97.2%;中空纤维反渗透膜在0.7 MPa、室温条件下,对0.5 g/L的NaCl水溶液通量可达12.2 L/(m~2·h),截留率96.5%.     

Preparation and heat resistance of hollow glass microbead/silicone rubber composite coating

Hollow glass microbead/silicone rubber composite coatings were prepared to improve the heat-resistance and mechanical properties of silicone rubber-based composites, using CE modified SR as the matrix and HGM as the filler. The microscopic morphology and thermal stability of the composites were characterized by scanning electron microscopy (SEM) and thermogravimetric analyzer (TGA), respectively. The results showed that the thermal stability of the composites increases with the increase of filler content. For the composite sample with a HGM mass content of 16.7%, the initial decomposition temperature (T₅) is 408°C, which is 84°C higher than that of silicone rubber. The low density and high sphericity of HGM make it easier to uniformly disperse in the polymer matrix. In addition, compared to silica, which is commonly used as an inorganic filler, the lower thermal conductivity of HGM is also beneficial for achieving better thermal shielding effect. It is confirmed that the insufficient thermal stability of the polymer matrix above 400°C can be compensated for by the properly dispersed inorganic fillers. Therefore, the thermal stability of the composite is improved by the synergistic effect of modified heat-resistant matrix and inorganic filler.     

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation (PV), poly (dimethylsiloxane)/ZIF-8 (PDMS/ZIF-8) coated polymeric hollow fiber membranes were studied in this research. First, PDMS was used for the active layer, and Torlon®, PVDF, Ultem®, and Matrimid® with different porosity were used as support layer for fabrication of hollow fiber composite membranes. The performance of the membranes varied with different hollow fiber substrates was investigated. Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers. The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated. The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect. Based on the result, ZIF-8 was introduced to prepare more selective separation layer, in order to improve the PV performance. The PDMS/ZIF-8/Torlon® membrane had a separation factor of 8.9 and a total flux of 847 g·m^-2·h^-1. This hollow fiber PDMS/ZIF-8/Torlon® composite membrane has a great potential in the industrial application.     

Pervaporative separation of butanol using a composite PDMS/PEI hollow fiber membrane

In the study, the separation and purification of butanol was carried out using the composite hollow fiber membrane having the active layer of polydimethylsiloxane (PDMS) on the macroporous support of polyetherimide (PEI). The pervaporation results with the initial butanol concentration showed a trade-off between flux and separation factor. However, both the flux and the separation factor increased as the operating temperature increased. The pervaporation results showed the butanol flux and the separation factor were higher than those of the reported results. In this study, butanol was concentrated by the pervaporation as a feasibility study for the biofuel applications.     

聚乙烯中空纤维离子交换膜的制备及应用进展

介绍了聚乙烯中空纤维阴离子交换膜、阳离子交换膜以及两性离子交换膜的制备方法和制备过程.首先采用光束或γ射线照射聚乙烯中空纤维膜表面产生自由基,然后改性单体与自由基反应引入预功能化基团,最后反应试剂与预功能基团进行化学反应制得中空纤维离子交换膜.同时,对制得的中空纤维离子交换膜在蛋白质分离、金属离子去除及酶固定反应方面的...     

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。     

Modified poly(vinylidene fluoride) hollow fiber composite membranes reinforced by hydroxyapatite nanocrystal whiskers

The modified poly(vinylidene fluoride) (PVDF) hollow fiber composite membranes reinforced by hydroxyapatite (HAP) nanocrystal whiskers were fabricated with wet‐spinning method. The PVDF/HAP/N‐methyl‐2‐pyrrolidone dope solutions experienced delayed demixing mechanism, and the precipitation rate slightly increased as the HAP whisker content increased. The cross sections of PVDF‐HAP and neat PVDF hollow fiber composite membranes were composed of five distinct layers: two skin layers, two finger‐like sublayers, and a sponge‐like layer. The Young's modulus of and tensile strength of the PVDF‐HAP hollow fiber membranes gradually increased with the addition of nano‐HAP whiskers. The elongation ratio was also improved, which was different from the polymeric membranes modified by other inorganic nanofillers. The permeation flux of the PVDF‐HAP hollow fiber membranes slightly increased with the increase of HAP content in the composite membranes as its hydrophilicity was improved. The crystallization behaviors of PVDF in the composite membranes were also investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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。     

Effects of coating solvent and thermal treatment on transport and morphological characteristics of PDMS/Torlon composite hollow fiber membrane

A new approach for formation of the polydimethylsiloxane (PDMS) layer on Torlon polyamide‐imide hollow fiber (PAI‐HF) support has been developed by directly after fiber spinning without the need to undergo the final conventional solvent exchange and drying step, thereby saving postspinning processing steps. The produced PDMS/PAI‐HF composite membranes were found to have high CO₂ permeance (i.e., 1100 GPU) and exhibited good CO₂/N₂ selectivities of 8–10 which is close to 90% of that of a PDMS dense film. The effects of coating solution, rewetting and crosslinking temperature on the PAI‐HF morphological features, that is, gas transport, skin thickness, skin integrity, and substructure resistance are investigated. The rewetting and thermal treatment of the PAI‐HF caused the densification of the skin layer and reduced the pore sizes on the top layer. In addition, the potential use of the PAI‐HF support with polymers that are insoluble in hexane is also considered. Effects of water, methanol, and hexane exposure of PAI‐HF to these solvents are considered. This evaluation calls attention to issues that must be addressed in any eventual use of the PAI‐HF with water‐soluble or methanol‐soluble selective layer polymers, rather than simple hexane‐soluble polymers such as PDMS. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45418.     

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。     

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].     

中空纤维膜的开发与应用进展

中空纤维膜作为一种特种纤维,近年来发展迅猛,已应用到各个领域。作者综述了中空纤维膜的开发与应用现状,包括中空纤维膜的发展历史、制备方法、改性方法及应用等几个方面,最后展望了中空纤维膜制备技术和应用领域的发展趋势。