电去离子过程脱除低浓度铜离子的研究

采用一级两段的膜堆,以模拟废水为对象,考察了电去离子(EDI)过程脱除低浓度铜离子的性能,为开发一种更环保更经济的重金属废水处理技术提供理论与实验基础.研究证实,脱除铜离子的EDI存在"增强传质"和"电再生"两种模式.在"增强传质"模式操作时,淡室的树脂保持为盐型,阴膜的浓室侧表面无结垢产生.在"电再生"模式下,树脂被水解离产生的H 和OH-所再生,EDI可将铜离子从 50mg/L 左右脱除至火焰原子吸收分光光度法无法检出,同时在阴膜浓室侧表面形成黑色的CuO结垢.选择适当的膜堆形式和工艺条件能够防止结垢,获得一个连续稳定的EDI过程.     

电去离子过程水解离机理的研究(Ⅲ)阴膜和阴树脂的降解对水解离的影响

通过对离子交换树脂与膜的污染与降解的分析,认为在常规的ED（电渗析）过程中,导致阴膜电阻增大并进一步诱发阴膜异常极化和水解离的主要因素是膜污染;而在电去离子（EDI）过程中,导致膜对电阻增大的主要因素则是阴膜和阴树脂的持续降解．根据弱碱性的叔胺化合物对阴离子交换膜的催化效应理论,对EDI过程浓缩水pH的演变认为阴膜和阴树脂一定范围内的逐渐降解过程,对应着其催化水解离反应逐渐加强的过程．此外,实验测定了EDI过程中阴阳离子交换膜的面电阻的变化情况,确证了阴膜降解反应的存在。     

电去离子(EDI)过程水解离机理的研究(Ⅱ)特征曲线的形成机理

在不同的工作阶段下,EDI过程特征曲线的形态均有所差异,主要表现在膜堆电流的减小和浓缩水pH的持续回升．从离子交换树脂和膜材料的角度出发,分析认为其原因主要在于过程中自然发生的,程度逐渐加强的阴膜和阴树脂的降解,此外,稳定工况下的V-I、pH-I特征曲线已不能形象和灵敏地表征EDI过程的工作状态,并提出了3种更实用的特征曲线概念用于EDI过程的表征、     

电去离子(EDI)过程水解离机理的研究(Ⅳ)ED和EDI过程水解离的差异性比较

ED和EDI过程中水的解离,在本质上均与高电势梯度有关,发生水解离时电势梯度的数量级为108V/m.在ED过程中,理论上阳膜先于阴膜发生浓差极化,但阳膜的极化与水解离在极化发生之后就受到膜面ζ-电位的制约,使得阳膜水解离反而远远滞后于阴膜.通过实验对EDI过程的水解离有了进一步的了解,并作了进一步分析,同时与ED过程的水解离现象作了对比.认为在EDI的淡水室内,填充的树脂使得不能形成具有抑制水解离效应的ζ-电位,从而阳膜先于阴膜发生水解离,且阴阳膜的水解离因更严重的浓差极化而更为剧烈.     

离子交换膜界面结构对膜电极性能影响的研究进展

燃料电池对我国能源转型具有深刻影响,膜电极(MEA)是其核心部件,对电化学装备性能起着决定性作用.其中,离子交换膜与催化层(CL)间的界面结构,直接影响MEA中反应与传质耦合过程.围绕离子交换膜的多种界面调控方法,及其在燃料电池中的应用展开论述,重点介绍了图案化离子交换膜、多孔离子交换膜和直接膜沉积3种技术途径.同时,通过分析离子交换膜界面结构对MEA性能的影响规律,阐述"界面结构-传质特性-膜电极性能"的关系.最后,对离子交换膜用于新型水电解制氢过程及未来发展进行展望.     

树脂分层填充EDI膜堆实验研究

介绍了阴、阳离子交换树脂分层填充EDI膜堆的特征,考察了一级两段式膜堆每段填充层数对EDI过程的影响.实验表明:每段填充2和16层的膜堆,在稳态条件下运行的电压一电流密度曲线呈现出一定的规律性;EDI膜堆浓水pH值随电流密度增加先下降后升高,最后稳定在碱性范围;两个膜堆均能在一定条件下持续、稳定生产17 MΩ·cm以上高纯水.最终,当两个膜堆在120 V下达到稳态运行时,填充的阴、阳树脂均具有一定的再生程度.     

电去离子(EDI)过程水解离机理的研究(Ⅰ)特征曲线

系统研究了电去离子（EDI）过程非稳态开机阶段及稳定工况下的特征曲线,获得了若干区别于电渗析（ED）过程特征曲线的重要现象。研究表明,在开机阶段,淡水室中水的解离主要是在阳膜／阳树脂的表面发生;随着过程逐渐达到稳态,阴膜／阴树脂的表面也将发生程度不断加强的水的解离,浓差极化与水解离的可利用性是EDI与ED过程的最本质区别。     

面向应用的膜蒸馏过程再探讨

讨论了膜蒸馏涉及的膜材料特性和应用中面临的问题.膜蒸馏过程实质属于传热控制过程,研究膜蒸馏过程的重点在于研究膜蒸馏过程中热量的传递与回收.吸收膜蒸馏传质过程无相变热损失,疏水膜兼具有传质与导热双重作用.采用曝气膜蒸馏工艺对反渗透浓水进行了连续高倍率浓缩,膜组件没有发生亲水化和膜污染问题,说明曝气膜蒸馏工艺在高盐度、易结垢的废水深度浓缩方面具有较好的应用潜力.水膜阻力本质是气体穿过多孔膜表面的气/液两相界面所需克服的界面张力,除了与膜材料本体特性、膜表面结构等因数有关外,还与气体传输方向有关.与传统中空纤维膜相比,设计的异形中空纤维多孔膜,断裂强力有很大的提高.将热泵技术与减压膜蒸馏过程耦合,热泵制热系数COP与蒸发器流速、冷凝器流速和膜蒸馏通量之间存在显著相关性.     

电去离子过程水解离的基本特征

通过考察EDI膜堆由非稳态到稳态的过程中浓水电导率的变化规律以及处于稳态条件下的V—I特性曲线，探讨EDI过程水解离的基本特征．研究表明，在膜堆内部离子一旦发生定向迁移，在树脂表面水界面层中就会形成较高的电势梯度，引起水的解离，而且在高电流密度下，淡室中离子交换膜表面水界面层也会发生水解离．     

低雷诺数下溴化锂溶液降膜吸收热质传递的数值研究

溴化锂溶液降膜吸收是吸收式空调系统中常见的热质传递形式之一。本文对溶液降膜吸收过程的热质耦合传递分析,建立了溴化锂溶液垂直降膜吸收热质传递的二维数学物理模型,采用CFD-Fluent对模型进行求解。计算得到不同Re下的液膜界面温度、液膜内浓度分布、传热传质通量及传热传质系数等。分析了Re对降膜吸收过程中热质传递的影响。结果表明:当液膜Re150时,液膜界面平均温度与平均传质系数随着Re的增大而增大,而平均传热系数随着Re的增大而减少;平均传热传质通量均是随着Re的增大而先增大后减小,存在一个最佳液膜Re使降膜吸收过程的传热传质通量达到最大,即Re=50时,平均传热和传质通量分别达到最大值7.2 k W/m~2与2.9×10~(-3)kg/(m~2·s)。     

1,3-丙二醇发酵液电渗析脱盐中离子膜影响的实验研究

电渗析法可以有效去除1,3-丙二醇发酵液中存在的有机酸盐,保证下游处理过程的顺序进行,为了选取适于该脱盐过程的离子膜种类,采用4种离子交换膜分别进行了发酵液电渗析实验,通过对脱盐效果的综合评价着重探讨了离子交换膜性能的影响、实验研究表明,对于有机酸盐电渗析脱除过程,阴膜的选取至关重要;当阴、阳膜导电能力较强时,脱盐效果良好,此外,进行了中性溶质在不同离子膜中的模拟扩散实验,在综合比较脱盐效果和中性溶质扩散损失的基础上,获得了针对1,3-丙二醇发酵液电渗析脱盐的较优阴、阳离子膜种类。     

Controlling Ion‐Transport Selectivity in Gold Nanotubule Membranes

We have developed a new class of synthetic membranes that consist of a porous polymeric support. This support contains an ensemble of gold nanotubules that span the complete thickness of the support membrane. The support is a commercially available microporous polycarbonate filter with cylindrical nanoscopic pores. The gold nanotubules are prepared via electroless deposition of Au onto the pore walls, and tubules that have inside diameters of molecular dimensions (<1 nm) can be prepared. Hence, these membranes are a new class of molecular sieves. We review in this paper the ion‐transport properties of these Au nanotubule membranes. We will show that these membranes can be cation‐permselective or anion‐permselective, and that the permselectivity can be reversibly switched between these two states. Ion permselectivity can be introduced by two different routes. The first entails chemisorption of an ionizable thiol, e.g., a carboxylated or ammonium‐containing thiol to the Au tubule walls. If the thiol contains both of these functionalities (e.g., the amino acid cysteine), the permselectivity can be reversibly switched by varying the pH of the contacting solution phase. Ion permselectivity can also be introduced by potentiostatically charging the membrane in an electrolyte solution. By applying excess negative charge, cation permselective membranes are obtained, and excess positive charge yields anion permselective membranes. In this case the permselectivity can be reversibly switched by changing the potential applied to the membrane.     

MicroITIES detection of nitrate by facilitated ion transfer

A microITIES array, created by laser photoablation of a 12-microm polyester film, was used to investigate electroassisted anion transfer between two immiscible electrolyte solutions. Besides measuring directly the transfer of nitrate to the organic phase, the enhancement of transfer of the cation (K+) by facilitated anion (counterion) transfer was measured as well. In the presence of a triamide derived from tris(2-aminoethyl)amine (tren), which is known to function as a host for nitrate, the current responses for both nitrate and potassium transfer were monitored. The linear relationships between the current responses and nitrate concentration formed the basis of an anion sensor with a dynamic range from 0.1 to 5 mM. A dual facilitated transfer mechanism is proposed to explain the enhancement phenomenon.     

基于交流阻抗法的离子交换膜电阻研究

利用交流阻抗谱测定技术,建立一种离子交换膜导电性能评价方法;使用两极室槽电解池,分别测得电解质溶液,以及膜和电解质溶液之和的电阻值,相减后得到离子交换膜在该电解液中的电阻值.通过并联电阻形成完整的半圆弧形交流阻抗谱,能够有效减小测量误差.利用硫酸水溶液体系、氯化钠水溶液体系,以及全钒液流电池的钒电解液体系验证基于交流阻抗谱的膜电阻测定技术准确性、实用性.在此基础上揭示阳离子交换膜、阴离子交换膜对离子的不同吸附特性,以及膜面电阻对电解质溶液浓度依存特性.研究结果对于发展离子交换膜快速表征技术,以及开发新能源领域的离子交换膜具有重要价值.     

Solidification of Boron-Containing Ion-Exchange Resins with Aluminosilicate Binder

Radiochemistry - Solidification of a mixture of ion-exchanger resins (IERs), consisting of a cation exchanger in the sodium form and an anion exchanger in the tetraborate form, using a binder based...     

Evaluation of the separate equilibrium processes that dictate the upper detection limit of neutral ionophore-based potentiometric sensors

The upper detection limit of polar ionophore-based ion-selective electrode membranes is predicted by utilizing the coextraction constant of dissociated electrolyte, the stability constant of the ionophore, and the membrane composition. The coextraction constant of dissociated electrolytes into the polar poly(vinyl chloride) membrane plasticized with o-nitrophenyl octyl ether (PVC-NPOE) is here measured by a novel approach. The sandwich membrane technique is utilized, with one membrane segment containing a lipophilic cation exchanger and the other containing an anion exchanger. This yields information about the coextraction constant and the free ion concentrations of the electrolyte in the two segments. Predictions correlate quantitatively with the upper detection limit observed for ion-selective electrodes based on the ionophores valinomycin, tert-butylcalix[4]arene tetraethyl ester, and calcimycin. The difficulties of the prediction of the upper detection limit for nonpolar poly(vinyl chloride) membranes plasticized with bis(2-ethylhexyl sebacate) (PVC-DOS) due to ion association are discussed in detail. A thermodynamic cycle experiment with a series of sandwich membranes shows that the principal processes governing the upper detection limit of PVC-DOS membranes are identical to those for the PVC-NPOE membranes. However, the stability of the ion pairs between the ionophore-metal ion complexes and the extracted anion are different from that of ion pairs formed between the same anion and the lipophilic anion exchanger. This makes it difficult to quantitatively predict the upper detection limit on the basis of simple apparent coextraction and complexation data alone. The approach reported herein is useful not only for mechanistic purposes but also to shed light onto the many cases where coextraction effects need to be understood but are not directly experimentally accessible.     

钒电池用离子交换膜的研究与开发

钒电池(VRB)是一种新型的高效储能电池.离子交换膜是VRB的核心部件之一.总结了VRB用离子交换膜在商业化膜(Nafion、PE-01、JAM等)改性处理及PVA、PVDF、PTFE基阳离子交换膜和ETFE、PPESK基阴离子交换膜研发等方面近4年来的技术进展,指出需重点关注高性能、低成本膜的开发,尤其是新型阴离子交换膜的研究与开发.     

pH-switchable, ion-permselective gold nanotubule membrane based on chemisorbed cysteine

An electroless gold plating method was used to deposit Au nanotubules within the pores of a polycarbonate template membrane. pH-switchable ion-transport selectivity was introduced by chemisorbing L-cysteine to the inside tubule walls. At low pH, where both the amino and carboxyl groups of the cysteine are protonated, these membranes preferentially reject cations and transport anions. At high pH, where both the amino and carboxyl groups are deprotonated, these membranes preferentially reject anions and transport cations. At pH = 6.0, near the isoelectric point of the chemisorbed cysteine, these membranes show neither cation nor anion transport selectivity. In addition to this electrostatically based selectivity, because of the small inside diameter of the Au nanotubules (as small as 0.9 nm), these membranes show molecular-size-based selectivity.     

Use of Raman spectroscopy to evaluate the selectivity of bifunctional anion exchange resins for perchlorate

Raman spectroscopy is used to evaluate the selectivity of two bifunctional anion exchange resins, Purolite A-530 and Amberlite PWA-2. It was found that the adsorption of anions on the resins is described by a Frumkin isotherm, which is determined by the ion pair constant, K, and the Frumkin parameter, g. The ion pair constant, K, is a measure of the strength of interaction between the resin and the anion and the Frumkin parameter, g, takes into account interactions between adsorbed anions. Although both resins have a polystyrene backbone and trihexylammonium and triethylammonium functional groups, the Purolite A-530 resin exhibits greater selectivity for perchlorate. The only discernable differences between the two resins is that the Amberlite PWA-2 has a higher trihexylamine content and the Purolite A-530 resin exhibits greater cross-linking. How the trihexylamine/triethylamine content and the degree of cross-linking affects the performance of these resins is discussed.     

以络合金属作催化剂的双极膜制备及电学性能

基于国内尚没有市售的良好双极膜,本研究以氯甲基化聚砜和磺化聚苯醚作为双极膜的阴阳膜层,在双极膜中间界面层固定络合金属作为催化剂,分别利用SnSO4、CrCl3、NiSO4作为催化剂制得3种双极膜,并与不添加任何催化剂制得的双极膜进行了比较.实验表明,络合金属对双极膜水解离有很好的催化作用,当中间界面层含有络合金属催化剂时,双极膜的水解离电势大大降低,并得到3种络合金属的催化活性为:Cr3+>Ni2+>Sn2+;过多催化剂用量会使双极膜的膜电阻增加;络合金属催化剂对双极膜的选择透过度影响不大,可以忽略;双极膜中间界面层中的络合金属催化剂与阴阳膜面的附着力不强,在酸碱环境中有些出现脱落或溶解.