Characterization of anion exchange membranes with natural organic matter (NOM) during electrodialysis

Natural organic matter (NOM) is thought to be a major source of fouling during membrane filtration of natural waters. The organic matter present in surface waters was characterized in terms of its molecular weight distribution, acidity and electrokinetic properties. The fouling potentials of anion exchange membranes were predicted by the characterization. Changes in the physicochemical properties of anion exchange membranes were also examined during electrodialysis (ED) process of solutions containing NOM. The ED performances were evaluated for the three anion exchange membranes (AMX, AM-1 and ACM) in the presence of NOM. Fouling phenomena in terms of current efficiency and NaCl flux were in good agreement with the fouling potentials predicted by the characterization results. Observations of the molecular weight distribution and the constituents of NOM revealed that the hydrophobic NOM fraction with high molecular weights deposited mainly on the membrane surface, providing fouling effects on the anion exchange membrane.     

Macroreticular anion exchange membranes for electrodialysis in the presence of surface water foulants

In this work two new types of anion exchange membranes having pore sizes of macro dimensions are described. Static and dynamic fouling resistance to common large anions found in surface waters is evaluated. Improvements over conventional microporous anion membrane types are discussed with respect to electrodialysis.     

Developing homogeneous ion exchange membranes derived from sulfonated polyethersulfone/N-phthaloyl-chitosan for improved hydrophilic and controllable porosity

Ion exchange membranes (IEMs) composed of sulfonated poly (ether sulfone) (SPES) and N-phthaloyl chitosan (NPHCs) were synthesized. NPHCs was employed in membrane fabrication to improve the porosity and hydrophilicity of membranes. The effect of blend ratio of sulfonation (DS) and NPHCs content on physico-chemical characteristics of home-made membranes was investigated. The morphology of prepared membranes was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD) and scanning electron microscopy (SEM). SEM images revealed the formation of a more porous membrane structure and smoother surface. The electrochemical and physical properties of CEMs were characterized comprising water content, contact angle, ion exchange capacity (IEC) and thermal stability. Membrane water content, surface hydrophilicity and IEC were enhanced with increase of DS and NPHCs blend ratios in casting solution. Furthermore, the diffusion coefficient was also improved slightly with increase of DS and NPHCs blend ratios in prepared membranes. Membrane potential, permselectivity, transport number and areal membrane resistance all showed decreasing trends by the increase in NPHCs blend ratio in casting solution. These results indicated that the prepared membrane has good prospective and great potential for desalination in electrodialysis applications.     

阴离子交换膜改性及抗污染性能研究进展

电渗析技术应用于工业废水脱盐时,废水中有机物及其它杂质组分等会造成膜污染,进而影响脱盐性能。电渗析膜污染防治对促进电渗析在工业废水处理中的应用有重要意义。相比于阳离子交换膜,阴离子交换膜更易形成有机污染,且更严重。阴离子交换膜污染主要由腐殖酸、牛血清蛋白、阴离子表面活性剂等有机物造成,污染过程主要受静电作用、亲和作用和几何因素的影响。膜改性提高阴离子交换膜的抗污染性能是电渗析膜污染防治的有效方法,目前已有许多有关膜改性提高阴离子交换膜抗污染性能的报道。膜改性方法主要有化学改性法、等离子体改性法、表面涂覆改性法、电沉积改性法、自聚合改性法及改进基膜结构法等。本工作对阴离子交换膜改性及抗污染性能的研究进展进行了综述,对不同改性方法的优缺点进行了分析和评价。这些改性方法能提高阴膜表面的负电荷密度和亲水性、降低膜表面粗糙度和基膜含水率等,因此可以改善阴离子交换膜的抗污染性能。然而,目前研究获得的改性阴离子交换膜仍存在修饰层不稳定、抗污染性能不理想和性能测试不系统等缺点,需进一步优化改性方法、改性工艺、组分修饰及性能测试等,以获得抗污染性能稳定且效果良好的改性阴离子交换膜。     

Removal of hardness in fermentation broth by electrodialysis

Lysine fermentation broth was desalinated by electrodialysis to reduce hardness concentrations as a pretreatment procedure for the purification and recovery of amino acids. Electrodialysis performance was investigated in terms of the rate of reduction in conductivity in dilute solutions and electrodialysis cell resistance for different ion exchange membranes at a constant current density. Among the membranes investigated in this study, membranes with high water content showed the better performance for hardness removal. Fouling experiments revealed that organics gave rise to fouling effects on the anion exchange membrane during demineralization of the lysine fermentation broth. The pulsed electric field with the half‐wave power enhanced the electrodialysis performances by mitigating membrane fouling in desalination of the lysine fermentation broth. This study successfully demonstrated the potential use of pulse power as an effective cleaning‐in‐place (CIP) method during electrodialysis of fermentation broth. © 2002 Society of Chemical Industry     

A study on fouling mitigation using pulsing electric fields in electrodialysis of lactate containing BSA

Fouling tendency in electrodialysis was investigated using the electrochemical and physical properties of the foulants and ion exchange membranes. It was found that bovine serum albumin (BSA), a large molecular weight protein, fouled the AMX membrane irreversibly by deposition on the membrane surface. Electrodialysis experiments of lactate with 1.0 wt% of BSA were performed using the square wave powers at different frequencies to examine the pulsing power influences as a fouling mitigation method, and the results were compared with the data obtained using the DC power. Reduced fouling potentials were observed when the square wave powers were used in the electrodialysis of lactate and confirmed the membrane fouling index for electrodialysis (EDMFI). The pulsing electric fields enhanced the mobility of the charged particles in the fouling layer and decreased the electric resistance of the electrodialysis cell. It was clearly observed that the pulsing electric fields with different frequencies reduced the fouling potentials, and consequently the power consumption was reduced significantly as a fouling mitigation method.     

工业废水电渗析过程中膜污染研究进展

综述了工业废水电渗析体系膜污染类型、性质、影响因素等的研究进展. 无机污染主要是Ca2+, Mg2+或其他高价离子在离子膜表面或内部形成的结垢现象,原理是极化或溶液过饱和形成沉淀. 有机污染是由蛋白、腐植酸、表面活性剂及大分子有机物在离子膜表面沉积或渗透到膜内部而形成,原因主要是带负电荷的有机物与阴膜荷正电基团的静电作用及带苯环有机物与基膜的亲和作用,其次是有机物分子大小与膜的网络结构的作用. 膜污染形成及其性质与施加电流、共存组分、温度、pH值和运行时间等密切相关,可造成离子膜导电性、离子交换容量、水含量和极限电流密度等减小,且有机污染对电渗析性能的影响比无机污染更严重. 由有机物凝胶层形成的膜污染可用电渗析膜污染指数定量描述.     

焦化生化出水电渗析脱盐研究

采用电渗析技术对焦化生化出水如曝气生物滤池出水及反渗透浓水进行脱盐,考察不同废水中的离子迁移、废水脱盐及离子交换膜污染情况。结果表明:2种焦化废水采用电渗析处理具有较好的脱盐效果,其中不同离子的迁移脱除与其浓度、离子半径等密切相关。膜电阻测试表明,不同焦化废水电渗析体系中不同离子交换膜的污染存在差别。扫描电镜和红外分析表明,曝气生物滤池出水主要由有机物造成阴离子交换膜污染,而反渗透浓水主要在电渗析浓室侧的膜表面形成颗粒状的无机污染,且阳膜浓室侧比阴膜浓室侧更显著。     

Structure–property relationships of anionic exchange membranes for Fe/Cr redox storage batteries

Membranes with lower area resistivity, higher selectivity, and reduced susceptibility toward fouling were required to improve the efficiency and lifetime of Fe/Cr redox storage batteries. The relationship of membrane structure to these electrochemical properties was not well understood. To gain a better understanding of structure–property relationships, a series of model membranes was synthesized in which the degree of crosslinking, ion exchange capacity, and porosity could be varied independently. This permitted the completion of several factorial studies in which the effect of each structural variable and interaction between variables could be defined and quantified. It was found that increasing the ion exchange capacity had a beneficial effect on all three electrochemical properties. Increasing the porosity reduced the resistivity and fouling but resulted in poorer selectivity. The degree of crosslinking had no effect on resistivity but improved selectivity and reduced fouling was observed when this parameter was increased. These relationships are consistent with theoretical models that have been proposed to account for the behavior of ion exchange membranes in general. From this data, empirical models were constructed which could be used to predict the area resistivity and water content of other anionic exchange membranes.     

Incorporating functionalized silica nanoparticles in polyethersulfone‐based anion exchange nanocomposite membranes

In order to investigate for anion exchange membranes (AEMs) with improved properties, four series of polyethersulfone‐based composite AEMs are fabricated by incorporating pristine and three functionalized silica nanoparticles containing propylamine, trimethylpropylamine, and melamine‐based dendrimer amine groups. The results show that by choosing appropriate functional agent, anion exchange membranes with improved parameters can be achieved. The polymeric matrix of the membranes is synthesized by chloromethylation of polyethersulfone using thionyl chloride followed by amination with trimethylamine (TMA). The effectiveness of chloromethylation process is confirmed by ¹H NMR analysis. The effects of functional groups on characteristic and transport properties of the prepared composite membranes i.e., SEM, IEC, water uptake, porosity transport properties, and conductivity are investigated. The scanning electron microscope images illustrates that the synthesized membranes possess dense structures. Ion exchange capacity (IEC), water uptake, transport properties, and conductivity of the composite membranes are measured. In addition, the morphology and thermal stability are characterized. IECs and ion conductivities of up to 1.45 meq g^?1 and 45.46 mS cm^?1 and moderate transport characteristics are obtained from the modified membranes which confirm that these membranes are appropriate for applying in electro‐membrane processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44596.     

Polarization studies on interpolymer ion exchange membranes

Polarization studies have been conducted for interpolymer ion exchange membranes by following the pH changes during electrodialysis from which the stagnant layer thickness was calculated. The pH changes are normal while an anion exchange membrane is used as a test membrane.     

Structural effects of ion‐exchange membrane on the separation of L‐phenylalanine (L‐Phe) from fermentation broth using electrodialysis

The effects of membrane structure on the separation of L ‐phenylalanine (L ‐Phe) by electrodialysis from a fermentation broth and on the fouling tendency were investigated in this study. Two anion‐exchange membranes (Neosepta AFX and AM‐1, Tokuyama, Japan) were selected and characterized using the chronopotentiometry method. For a fresh membrane, AFX showed a lower electrical resistance and a lower permselectivity than AM‐1. After being fouled with humic acid, however, the electrical resistance of AFX was higher than that of AM‐1. The L ‐Phe selectivities for both membranes were lower than those of the fresh membranes. The result may be attributed to the structural difference between AFX and AM‐1 membranes. AFX has a lower repulsion force against the co‐ion and could be more strongly affected by the foulants than AM‐1 because AFX has a more porous structure than AM‐1. Experiments on the separation of L ‐Phe from the fermentation broth were carried out using two different stack configurations, ie desalting electrodialysis and water‐splitting electrodialysis. It was observed that the recovery efficiency of L ‐Phe through electrodialysis for 100 min reached 95% for AFX and 85% for AM‐1. In the desalting configuration of electrodialysis, the solution pH must be adjusted to alkaline conditions to recover the L ‐Phe through the anion‐exchange membrane. On the contrary, it was possible to recover the L ‐Phe without adjustment of the solution pH in the water‐splitting electrodialysis because OH^? generated from the bipolar membrane converted neutral L ‐Phe into an anion. © 2002 Society of Chemical Industry     

Electrodialytic removal of nitrates and hardness from simulated mixtures using ion‐exchange membranes

A novel electrodialysis (ED) pilot plant unit coupled with a membrane stack containing 11 cation‐exchange and 10 anion‐exchange membranes is used for the removal of nitrates and hardness from simulated aqueous mixtures containing salts that are usually encountered in brackish water. The removal of high nitrates and water hardness is performed in 150 min of ED under three constant applied voltages at room temperature. The limiting current density is obtained for sodium nitrate and calcium chloride mixtures in dilute solution. In order to check the efficacy of the ED method, parameters like the applied potential are varied at constant flow rates. The efficiency of the ED method depends on the applied potential. Possible applications of ED are discussed for the removal of contaminants below the minimum contaminant level of drinking water. The ED method used here is satisfactory to produce good quality drinking water from a simulated mixture by removing the unwanted ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1788–1794, 2006     

硅溶胶辅助制备Beta分子筛膜

采用二次生长法，通过在晶种涂覆液中添加硅溶胶，在不锈钢丝网载体上制备牢固的Beta分子筛膜，系统考察晶种层中硅溶胶含量、晶种涂覆量、结晶温度和结晶时间对分子筛膜生长的影响。实验中发现，硅溶胶的存在可以增加涂覆层的牢固度，促进Beta分子筛膜的生长；硅溶胶既具有黏合剂的作用又可以补充硅源。当涂覆量较低时，无法得到一个完整的分子筛膜，分子筛膜负载量随着涂覆量的增加而增加；当结晶温度升至一定程度，分子筛膜组成不再单一。晶化过程中伴随着晶种的脱落和溶解。制备的Beta分子筛膜对N₂O催化分解具有良好的催化活性。     

Improved antifouling of anion-exchange membrane by polydopamine coating in electrodialysis process

The fouling, in particular the organic fouling of anion exchange membranes (AEMs), is a serious problem in electrodialysis (ED). In this paper, we attempted to improve the antifouling potential of AEM by surface modification with polydopamine (PDA). The antifouling potential was evaluated by the transition time, i.e. the time elapsed before fouling took place, using sodium dodecyl benzene sulfonate (SDBS) as a model foulant. The negative surface charge density, hydrophilicity and roughness of the membrane surface were increased with increasing dopamine concentration in the modification solution. The increases in negative surface charge density and hydrophilicity increased the antifouling potential, while the increase in surface roughness decreased the antifouling potential. Consequently, the optimum modification condition was the immersion into a 0.1 kg/m³ dopamine aqueous solution at pH 8.8 for 24 h. Under this condition, the antifouling potential of AEM was sufficiently improved. It was shown by theoretical analysis of the fouling data that the surface modification with PDA prevented the adsorption of SDBS micelles and improved the antifouling potential. Furthermore, it was experimentally confirmed that the modified membrane was highly stable.     

PEI交联的PECH/nylon复合阴离子交换膜的制备及性能研究

聚环氧氯丙烷（PECH）是一种线性高分子聚合物,具有较好的稳定性和成膜性能,且以PECH为基体制备阴离子交换膜,可避免致癌物质如氯甲醚、双氯甲醚的使用,但存在机械强度差与吸水性较大等缺点。本研究采用聚乙烯亚胺（PEI）作为交联剂,通过其与PECH发生交联反应,在其内部形成网状结构限制PECH膜在水中的过度溶胀,从而增强膜的机械强度,同时引入尼龙网布（nylon）作为支撑材料进一步提高膜的力学性能,制备了QCPECH/nylon复合阴离子交换膜。研究结果表明,制备的P1膜在电渗析应用过程中的脱盐效率（94.8%）比商业膜（Neosepta AMX）的脱盐效率（92.4%）更高,由此可见,用PEI交联的PECH/nylon复合阴离子交换膜在电渗析脱盐中具有潜在的发展前景。     

Performance studies of heterogeneous ion exchange membranes in the removal of bivalent metal ions in an electrodialysis stack

Heterogeneous anion and cation exchange membranes have been prepared by solution casting technique with poly(vinyl chloride) as inert binder and anion/cation exchange resins (?300 + 400 mesh) in a blend ratio of 60 : 40. The membranes were characterized with respect to their physical, mechanical, and electrochemical behavior. Anion and cation exchange membranes (10 cell pairs) were packed in an electrodialysis stack in a parallel plus series flow pattern. Desalting experiments were carried out with four different salt solutions, such as calcium chloride, magnesium chloride, cupric chloride, and nickel chloride (varying in their total dissolved solid from 500 to 1000 ppm), at different applied potentials and flow rates. The resultant current, percentage reduction in total dissolved solid, current efficiency, and energy consumption were calculated. The maximum current density in the electrodialysis stack was observed for calcium chloride solution and at any applied potential and flow rate the percentage reduction in total dissolved solid for Ca⁺⁺ > Cu⁺⁺ > Ni⁺⁺ > Mg⁺⁺. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Investigation of pore structure of ion exchange membranes

The pore structure of heterogeneous ion exchange membranes was studied by the mercury penetration method using a commercially available apparatus. Results obtained from the porosymmetrical measurements show that the membranes possess two layers, the upper one being less porous than the lower backing layer. The distribution of the pores in width and length is non-homogeneous. Anion exchange membrane MA-41 has a relatively more homogeneous pore structure.Application of the mercury penetration method makes it possible to quantitatively assess the degree of mechanical destruction of anion exchange membranes during the working period. It was found that membranes operated at the cathode and anode compartments of the electrodialysis unit are destroyed more quickly.     

Development of quaternarized poly(vinyl alcohol) anion‐exchange membranes for applications in electrodialysis

The main objective of this work is the development of anionic exchange membranes for the treatment of solutions containing metallic ions using the electrodialysis process. Anionic membranes were synthesized from poly(vinyl alcohol), with the insertion of quaternary ammonium groups in the polymeric matrix and subsequent crosslinking with glutaraldehyde and maleic anhydride. Different membranes were synthesized in order to evaluate the combination of physical–chemical properties and ionic transport. The morphology and structure of the membranes were investigated by scanning electron microscopy and infrared spectroscopy. The thermal transitions and stability of all the membranes were characterized using calorimetric techniques: thermogravimetric analysis, and differential scanning calorimetry, and compared with those of the individual polymers. The physical properties (ion‐exchange capacity, water absorption, and dimensional stability) showed that the different crosslink agents used significantly affect the membrane properties. The electrodialysis performance of the membranes in the transport of chloride and nitrate ions showed that the membranes produced can be successfully used in this separation process. Selemion® AMV commercial membrane was used to compare the percentage extractions of the indicated ions with the produced membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44946.     

Anion exchange membranes prepared from chloromethylstyrene and 2-methyl-5-vinylpyridine

Strongly basic anion exchange membranes were prepared by the radical copolymerization of chloromethylstyrene and 2-methyl-5-vinylpyridine. The formation of a three-dimensional structure and the presence of the quarternary pyridinium group were confirmed by infrared spectrum analysis and its strongly basic anion exchange properties. Their electrochemical properties and morphology were compared with those of the anion exchange membranes prepared from chloromethylstyrene-divinylbenzene and 2-methyl-5-vinylpyridine-divinylbenzene. The chloromethylstyrene-2-methyl-5-vinylpyridine membranes were proved to have larger anion exchange capacity, smaller electric resistance, larger water content, and higher permeability than the chloromethylstyrene-divinylbenzene and 2-methyl-5-vinylpyridine-divinylbenzene membranes. Also, the membranes have heterogeneity in the cross-linking structure.