A computer simulation of batch ion exchange membrane electrodialysis for desalination of saline water

A computer simulation program is developed for predicting desalinating performance of a batch electrodialysis process. The program includes the principle of ① mass transport, ② current density distribution, ③ cell voltage, ④ mass balance/energy consumption and ⑤ limiting current density. In this simulation the following parameters are inputted; ① membrane characteristics such as overall transport number, overall solute permeability, overall electro-osmotic permeability, overall hydraulic permeability, direct current electric resistance etc., ② electrodialyzer specifications such as flow-pass thickness, flow-pass width and flow-pass length in a desalting cell etc. and ③ electrodialytic conditions such as voltage, electrolyte concentration in a feeding solution, linear velocity in desalting cells, standard deviation of normal distribution of solution velocity ratio etc.The following phenomena were computed and discussed; ① Changes of electrolyte concentration and current density with operation time. ② Influence of cell voltage on operation time (batch duration), water recovery and energy consumption. ③ Influence of volume of an electrolyte solution prepared at first on operation time. ④ Influence of cell voltage, electrolyte concentration and standard deviation of solution velocity ratio in desalting cells on limiting current density. ⑤ Energy consumption in a reverse osmosis process. ⑥ Excepting limiting current density, the performance of an electrodialyzer is never influenced by the standard deviation of normal distribution of solution velocity ratio in desalting cells. ⑦ Energy consumption in electrodialysis is less than that in reverse osmosis at feeding saline water concentration less than about 2000 mg/l.     

电渗析苦咸水淡化技术研究进展

电渗析苦咸水淡化技术具有脱盐效果好、成本较低、绿色环保等优点,但存在制膜工艺繁琐、传质模型不够精确、能效有待提升等问题。本文首先分析了苦咸水电渗析用离子交换膜的制备及改性方法,对膜材料存在的问题进行了探讨。综述对比了苦咸水电渗析在简化模型、理论模型、半经验模型方面的原理及最新进展,系统总结了常规苦咸水电渗析过程的运行方式和工艺优化策略,并进一步介绍了以新型电去离子、冲击电渗析、可再生能源驱动电渗析为代表的新型电渗析过程在苦咸水淡化方面的原理及应用。在此基础上,提出了今后的研究方向集中于降低制膜成本、优化传质模型、探究集成膜法淡化工艺以及新型电渗析过程等方面。     

电渗析脱盐过程离子传递现象的数值模拟

建立了电渗析脱盐过程离子传递稳态模型,研究了离子电荷数、离子扩散系数和离子交换膜电导率对脱盐过程传质的影响,描述了离子浓度分布、电势分布和离子传递通量分布的变化情况。研究表明:相较于一价离子,二价离子在电渗析过程中膜两侧浓度差较小,跨膜电压降较高,各项传递通量较小;当离子扩散系数增大时,膜两侧浓度差减小,跨膜电压降升高,总传递通量和电迁移通量增大;当离子交换膜电导率增大时,膜两侧浓度差增大,跨膜电压降降低,各项传递通量均增大。     

Determination of the limiting current density in electrodialysis desalination as an empirical function of linear velocity

Electrodialysis is known to be a useful membrane process for water desalination. The limiting current density (LCD) in the electrodialysis process is an important parameter which determines the electrical resistance and the current utilization. Usually, LCD depends on membrane and solution properties as well as on the electrodialysis stack construction and various operational parameters such as the flow velocity of the diluate solution. Therefore, a reliable determination of LCD is required for designing an efficient electrodialysis plant. In this study, LCD was measured in an electrodialysis flow cell system of given geometry and spacer configuration as a function of the linear velocity. The coefficients a and b of an equation describing LCD as a function of the linear flow velocity of the diluate solution, i_lim=aCu^b, were determined from a plot of the measured LCD over the electrolyte concentration versus the linear velocity on a double logarithmic scale. It was found that the coefficient b was related to the hydrodynamic conditions, while the coefficient a was affected by the cell geometry, electrolyte concentration and the membrane properties.     

电渗析用季铵化聚氯乙烯均相阴离子交换膜的制备

以1-甲基咪唑(N-MI)为季铵化试剂一步法对聚氯乙烯(PVC)功能化改性，并制备了均相PVC阴离子交换膜，避免了传统阴离子交换膜制备过程中的氯甲基化步骤。通过对比研究，优化后的PVC-N-MI-5表现出较好的综合性能。离子交换容量和迁移数分别高达2.89 mmol·g^–1和98.4%；吸水率和溶胀率分别为4.24%和0.21%，低于商业JAM-5阴离子交换膜(4.87%和3.33%)；脱盐率、电流效率以及能耗分别为98.38%、55.8%和5.1 kW·h·(kg NaCl)^–1，可与商业JAM-5(93.0%、55.2%和4.6 kW·h·(kg NaCl)^–1)相比较。低廉的原料与简便的制备过程以及相对良好的电渗析应用性能，表明所制备的PVC-N-MI-5具有一定的应用前景。     

Ion and water transport properties of cation exchange membranes prepared by heavy-ion-track grafting technique

ABSTRACT

For high-performance electrodialysis of saline water, cation exchange membranes (CEMs) that actively transport Na⁺ and restrict water permeation are required. In this study, we prepared novel CEMs by a heavy-ion-track grafting technique and measured their membrane resistance and water permeation flux as transport properties. The prepared nanostructured CEMs exhibited lower resistance and lower water flux than the commercial CEM. Na⁺ ions were efficiently transported through their unique one-dimensional ion channels (low resistance), while water transport was suppressed due to the very low water uptake of the CEMs. These results demonstrated the high potential of these nanostructured CEMs for use in practical saline water electrodialysis.     

Studies on integration of ion exchange and nanofiltration for water desalination

This work addresses an integrated treatment to produce drinking water involving the ion exchange (IEX) and nanofiltration processes. In the first stage, the experimental procedure consisted of evaluating the IEX equilibrium and the dynamics of fixed-bed saturation/regenerations, for the system Cl^?/SO₄², using an anionic resin, Purolite A850, in the form sulphate. A mathematical model which considers axial dispersion for the liquid phase and linear driving force for intraparticle mass transfer predicted well the breakthrough curves of Cl^? and SO₄^2?. In the second stage, the selective separation of Cl^?, Na⁺ and SO₄^2? ions through a flat membrane nanofiltration TS80 was assessed.     

Separation of small organic ions from salts by ion‐exchange membrane in electrodialysis

Electrodialysis (ED) can be applied in the food and fermentation industry for separating inorganic salts and organic ions from other fractions. However, the separation efficiency for small organic ions should be understood in detail. In this article, the membrane selectivity and transport mechanism of small organic ions from mixed salts by ion‐exchange membranes are theoretically and experimentally investigated. First of all, the influence of current density on the solute flux (organic ions and inorganic ions) and on membrane selectivity (between organic ions and inorganic ions and between different organic ions) in ED has been studied. The selectivity was shown to be influenced by changing the applied current density. It was observed that separation of inorganic ions from organic solutes was feasible, but the selectivity was dependent on the size, charge, and functional groups of the organic ions. Furthermore, results imply that binary organic anions with larger molar mass (>130, i.e., aspartate and tartrate) can be adsorbed onto the membrane free volume and hence form a charged double layer, which affects membrane selectivity. Finally, competition between small organic and inorganic ions is discussed by comparison of the concentration profiles and current efficiencies of the different anions. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Characterization of cation‐exchange membrane fouling during bipolar membrane electrodialysis of monosodium glutamate isoelectric supernatant

BACKGROUND: A novel procedure that involved regeneration and recycling of ammonia and sulfuric acid from monosodium glutamate isoelectric supernatant with bipolar membrane electrodialysis (BMED) was proposed. As the performance of the membranes deteriorated during the batch runs, fouling of the cation‐exchange membrane (CEM) in contact with the base cell was studied. RESULTS: During ten consecutive batches of BMED, some operating parameters deteriorated gradually. Using scanning electron microscopy observations, fouling deposits were found on the CEM surface on the base cell side. Using Fourier transform infrared spectroscopy and reversed‐phase high‐performance liquid chromatography (RP‐HPLC), the organic fouling fraction of the CEM foulants was found to contain eight amino acids. Using X‐ray energy‐dispersive analysis, the mineral fouling fraction was shown to be mainly O and Ca elements, and a little Mg. Using X‐ray diffraction, the inorganic foulant was identified as CaCO₃, mainly in the form of calcite and a little aragonite. CONCLUSION: The CEM was subject to membrane fouling consisting of an organic fouling fraction and a mineral fraction. The organic fraction occurred as ions with some positive charges from the isoelectric supernatant and probably existed in the form of amino acids or their peptides. The mineral fraction was mainly CaCO₃ calcite and aragonite, and probably a little amorphous Ca and Mg hydroxides. Copyright © 2011 Society of Chemical Industry     

反渗透海水淡化膜法预处理技术研究进展

简要论述了反渗透海水淡化的各种新型膜法预处理技术研究进展情况及其在国内外的具体运用情况,内容主要涵括连续微滤技术(CMF)、浸没式帘式膜过滤、超滤技术、纳滤技术以及陶瓷膜过滤.并指出膜法预处理将成为今后反渗透海水淡化预处理的主要发展方向.     

Synthesis and characterization of new proton exchange membrane deriving from sulfonated polyether sulfone using ionic crosslinking for electrodialysis applications

In this research work, the synthesis and characterization of new ion exchange membranes made from sulfonated polyether sulfone (S PES) crosslinked by aminated PES (NH2 PES) crosslinking reagent have been investigated for electrodialysis (ED) applications. Sulfonated and aminated PES have similar chemical structures that allow a good compatibility, the only difference between them is their functional groups. This membrane (called HNH2) has been obtained by reaction between S PES with 1.3 SO₃H groups per monomer unit and the calculated equivalent amount of NH2 PES. Three HNH2 membranes have been fabricated with different degrees of sulfonation. The HNH2 membranes properties have been evaluated using different characterization analysis. The results have shown that HNH2 membranes appear to be very promising candidates for electrochemical applications.     

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。     

Separation of strontium and cadmium ions from nitrate medium by ion‐exchange membrane in an electrodialysis system

The separation of strontium and cadmium ions in a system containing ethylenediaminetetraacetic acid (EDTA) as a complexing agent has been studied using a three‐compartment electrolytic cell. The results suggest that under the influence of an electric field, Sr ions were exclusively transported to the cathode as positively charged uncomplexed cations while cadmium ions removed from the middle compartment of the electrolytic cell migrated to the anode as negatively charged complexes. The effect of the EDTA complexing agent on the separation was studied within the pH range 2–4 at 100 mA (12.4 mA cm^?2). Copyright © 2003 Society of Chemical Industry     

质子交换膜燃料电池膜中气态水管理模型

分析质子交换膜燃料电池的膜水含量与运行参数的关系,从工程方法的角度建立水传输模型.模型分析得到,要提高膜的水合程度,需要通过增湿反应气体.过高的增湿反应气体又会引起阴极扩散层水的泛滥,需通过调节反应气体流量来缓解水的泛滥.为保证膜的高水合程度和低的阴极扩散层水的泛滥,建立了膜水含量的神经网络控制模型,为电池水管理奠定了基础.     

Antifouling membrane based on sodium alginate coated polyamide thin film composite for desalination of brackish water

Sodium alginate coated polyamide thin film composite (SA/PA-TFC) membranes were synthesized for the desalination of brackish water through reverse osmosis. Membranes were characterized by Fourier transform infrared spectroscopy, x-ray diffraction, scanning electron microscopy, AFM, thermogravimetry, and universal testing machine for structural analysis, crystallinity, morphological, compositional, thermal, and mechanical properties, respectively. The effect of feed pressure on water flux and % salt rejection was quantified. Simulation results generated using the commercial process simulator PRO/II were in good agreement with the experimental data. Case studies using simulator were performed for brackish water with different salinity to optimize operating pressure based on product unit cost (PUC) by varying the feed pressure and membrane area. The calculated PUCs were found to be 0.9 and 0.3 $/m³ for corresponding feed total dissolved solids (TDS) concentrations of 5000 and 500 mg/L at an optimum pressure of 10 bar, to achieve a salt rejection of 98% using a membrane area of 335 m². We believe these membranes are a prospective solution for brackish water desalination.     

A new derivation and numerical analysis of current-voltage characteristics for an ion-exchange membrane under limiting current density

Based on the Nernst-Planck equations of ion flow, a simple model was proposed for the current-voltage characteristics of an ion-exchange membrane under limiting current density. The numerical analysis depicts the influence of parameters such as solution concentration, diffusion boundary layer thickness, diffusion coefficient and transport number in solution and in membranes on current-voltage curves, as well as the profiles of the concentration and potential in membrane phase and in diffusion boundary layers. Limiting current density is discussed with the parameters and is consistent with the well known expressions. This work can be regarded as a supplement of the previous studies by Spiegler [Desalination, 9 (1971) 367] and Mafé [Journal of Membrane Science, 61 (1991) 177].     

A simple determination of counter-ionic permselectivity in an ion exchange membrane from bi-ionic membrane potential measurements: permselectivity of anionic species in a novel anion exchange membrane

A new method is proposed here for determining counter-ions permselectivity through an ion exchange membrane. The theoretical base of the method is Henderson equation. After simplifying at special experimental conditions, a linear relationship between the bi-ionic membrane potential term and concentration ratio, i.e., [exp(z_AF(−ΔE_T)/RT)−1]∝[C_A,L/C_B,L] can be obtained, from the slope of which, the permselectivity of counter-ions can be achieved. This method is very simple in operation and less time and money consuming. The method is exemplified by common 1–1, 2–2 and 2–1 counter-ions pair through a novel and published anion exchange membrane. The accuracy and the validity of the method is tested by three aspects: (1) the experimental [exp(z_AF(−ΔE_T)/RT)−1]∝[C_A,L/C_B,L] curve approaches a straight line (2) the predicted order of counter-ions conforms to the results evaluated in a practical electrodialysis process; and (3) the results calculate from different referenced counter-ions for the same counter-ions pair agree well with each other.     

离子交换膜技术处理冶金工业废液的研究与应用

离子交换膜技术是一种很有潜力的分离方法，在废水处理方面有广阔的应用前景。作者综述了电渗析法、离子膜电解法和扩散渗析法等离子交换膜技术处理冶金工业废液的研究与应用现状。该技术不仅节能、工艺简单、节省原料、不会产生二次污染，还能实现盐的电化学分解，使组分充分回收，而且设备简单紧凑，易于操作。但该技术要实现工业化必须针对冶金工业废液的特点，加强离子膜合成的研究，改进离子膜装置，使研究与应用相互促进。     

The determination of diffusion coefficients of counter ion in an ion exchange membrane using electrical conductivity measurement

Electrical conductivity experiments were carried out in a bi-ionic (chloride-nitrate) electrolyte with and without a permselective anion exchange membrane (ACS of Tokuyama Soda) at variable chloride/nitrate concentration. Diffusion coefficients of counter ions (Cl⁻ and NO₃⁻) in the membrane were determined from a mathematical model based on the Nernst-Planck diffusion-convection theory: the mean diffusion coefficients in the membrane were obtained by fitting the (conductivity vs. concentration) curves with the Nernst-Planck equation.     

Preparation of mineral source water from deep sea water: Reduction of sulfate ion using selemion ASV membrane

Adopting a laboratory‐scaled electrodialysis (ED) process, we investigate the performance of a monovalent anion exchange permselective membrane in the reduction of the concentration of sulfate ions during the production of mineral source water from deep sea water (DSW). The dependence of the separation efficiency of anions on the operating time and the applied DC voltage is investigated based on a brine having salinity of about 15% prepared from DSW. The experimental results reveal that if the applied DC voltage is high, the change in the liquid volume during ED is dominated by the ions transported and the effect of electroosmosis. In addition, the amount of chloride ions transported correlates roughly linearly with the operating time, and the transport of sulfate ions is found to be blocked by chloride ions, presumably because of that the pore size of the permselective layer is close to the size of sulfate ions. © 2010 American Institute of Chemical Engineers AIChE J, 2011