膜法电容去离子技术用于水溶液中单/多价阴离子的分离

将电容去离子技术(CDI)与单价阴离子选择性交换膜结合构建新型膜法电容去离子膜堆(PSMCDI),并探索其在单/多价阴离子分离中的应用。采用自制的测试装置,以Cl-/SO42-水溶液为模拟体系,并选择现有的两种商业化单价阴离子选择性交换膜(ASV和ACS)作为膜元件,系统地研究了各参数(PSMCDI种类、阴离子组成和浓度、pH、操作时间、电压和流速)对单价离子选择性的影响。结果表明,总阴离子去除量随着阴离子浓度的增加而增加,但是对于单价离子(Cl-)选择性降低。随着操作时间的增加,单价离子(Cl-)选择性也降低。对于ASV膜,在1.2 V的直流电压、10 min吸附时间和30 ml·min-1进料流速的条件下得到1.6的单价阴离子去除选择性。同时,在相同条件下,ACS膜的单价阴离子去除选择性为1.4。     

单价选择性阴离子交换膜的改性研究进展

详细介绍了表面改性法和膜基体改性法的原理、特点及其改性效果，总结了近3年来单价选择性阴离子交换改性的研究进展并对不同改性方法进行了评价。结果表明，膜改性是一种提高单价选择性阴离子交换膜的渗透选择性、离子通量和抗污染性能的有效方法。最后分析了限制单价选择性阴离子交换膜量产的因素，并展望了单价选择性阴离子交换膜可能的量产方向。     

含哌啶阳离子侧长链型一/二价阴离子选择性分离膜的制备

基于超酸催化聚合机理制备了含咔唑片段的聚合物主链结构,并通过调控季铵化反应中N-甲基哌啶单体的用量,得到了不同哌啶离子含量的阴离子选择性分离膜。通过核磁共振氢谱证明了聚合反应和季铵化反应顺利进行。热重和动态机械分析的测试结果表明膜具有优异的热稳定性和力学性能。通过电渗析 （ED） 测试膜的阴离子分离性能,结果显示离子通量和选择性均优于商业膜Neosepta ACS。在NaCl/Na₂SO₄体系中,QPC-Pip-60的Cl^-通量可达3.24 mol·m^-2·h^-1,选择性可达11.6。在NaOH/Na₂WO₄碱回收体系下,良好的微相分离结构使得OH^-通量可达3.59 mol·m^-2·h^-1,选择性最高为70。长时间稳定性测试和碱稳定性测试结果表明所制备的系列膜具有优异的循环稳定性和耐碱性能。     

含哌啶阳离子侧长链型一/二价阴离子选择性分离膜的制备

基于超酸催化聚合机理制备了含咔唑片段的聚合物主链结构,并通过调控季铵化反应中N-甲基哌啶单体的用量,得到了不同哌啶离子含量的阴离子选择性分离膜。通过核磁共振氢谱证明了聚合反应和季铵化反应顺利进行。热重和动态机械分析的测试结果表明膜具有优异的热稳定性和力学性能。通过电渗析 （ED） 测试膜的阴离子分离性能,结果显示离子通量和选择性均优于商业膜Neosepta ACS。在NaCl/Na₂SO₄体系中,QPC-Pip-60的Cl^-通量可达3.24 mol·m^-2·h^-1,选择性可达11.6。在NaOH/Na₂WO₄碱回收体系下,良好的微相分离结构使得OH^-通量可达3.59 mol·m^-2·h^-1,选择性最高为70。长时间稳定性测试和碱稳定性测试结果表明所制备的系列膜具有优异的循环稳定性和耐碱性能。     

Fe3+诱导聚多巴胺-聚乙烯亚胺电沉积制备单价选择性膜

仿生黏合剂聚多巴胺(polydopamine,PDA)与聚乙烯亚胺(polyethyleneimine,PEI)共沉积是构建单价选择性分离层的有效方法。本实验通过浸泡预处理将Fe³⁺引入阳离子交换膜，并利用电场作用和Fe³⁺诱导PDA-PEI在膜面沉积改性。结果表明，该方法大大缩短了单价选择性膜的改性时间，制备了单价选择性阳离子交换膜。利用扫描电子显微镜、紫外可见分光光度计、红外光谱仪、zeta电位对制得的膜进行表征和性能测试，探讨了Fe³⁺浓度对改性膜性能的影响。表明随着Fe³⁺浓度的增加改性膜的膜电阻呈上升趋势，而表面荷正电性和选择性均呈先增加后降低的趋势。由于电场和Fe³⁺对多巴胺聚合过程的共同影响，当Fe³⁺的浓度为0.001mol/L时，改性膜Na⁺/Mg²⁺选择性高达12.8，并且具有较低的膜电阻和优异的稳定性。     

离子色谱法测定黄花草木犀中Cl-、NO3-和SO42-的含量

目的建立离子色谱法测定黄花草木犀提取物中Cl^-、NO₃^-和SO₄^2-的含量。方法采用去离子水对药材进行超声提取,采用离子色谱法对提取物进行测定,色谱柱为DionexIonPacAS22型分析柱,流动相为超纯水-Na HCO₃(1.5mmol·L^-1)-Na₂CO₃(4.5mmol·L^-1),等度洗脱,流速为1.2mL·min^-1,柱温为27.2℃。结果Cl^-、NO₃^-和SO₄^2-的离子浓度与色谱峰面积具有良好的线性关系,相关系数分别为0.9993,0.9995,0.9991,样品低、中、高加标回收率在90%～105%之间。结论该方法稳定性好,灵敏度高,操作简便,适用于测定黄花草木犀中阴离子的含量。     

共存物质对UV/PS降解莠灭净的影响及降解路径

采用紫外（UV）激活过硫酸盐（PS）生成活性极强的自由基（·SO₄^-、·OH）降解莠灭净（AMT）,考察了UV/PS工艺对AMT降解效果及反应动力学模型。研究了水中不同浓度的无机阴离子（Cl^-、HCO₃^-、NO₃^-）、天然有机质（腐植酸）对反应效果及速率的影响,比较了超纯水、自来水和锡东水厂不同工艺出水作为不同水质背景时AMT的去除效率,并推测了UV/PS降解AMT的降解产物及可能的降解路径。结果表明：UV/PS对AMT的降解符合准一级反应动力学模型（R²≥0.94）。水中Cl^-浓度为5mmol/L时,会抑制AMT的降解,而其他浓度的Cl^-对反应的影响并不明显;随着HCO₃^-浓度的增加,准一级反应速率常数k_obs逐渐减小;NO₃^-会加快AMT的去除,当其浓度为200mmol/L时对AMT降解的促进作用变弱;随着腐植酸质量浓度的增加,k_obs逐渐减小。AMT在超纯水中的降解率高于其他实际水体中的降解率。UV/PS系统降解AMT过程中主要的降解产物可能是2-甲硫基-4,6-二氨基-1,3,5-三嗪和2-羟基-4-乙氨基-6-异丙氨基-1,3,5-三嗪。     

电容法选择性去除水体中有害离子

选择性去除污水中的有害离子对污水净化和资源回收有重要意义。而电容去离子技术（CDI）作为一种新型水处理技术,在有害离子选择性去除方面具有独特的优势和广阔的应用前景。通过电极材料开发、离子交换膜/树脂在CDI中的引入及CDI操作条件的优化,可以有效提高CDI的离子选择去除性能。按照优化途径,综述了CDI技术选择性去除目标污染物的研究进展,以期为CDI技术选择性去除目标离子的进一步研究提供参考。     

动态电渗析膜工艺对酸性冷轧废水的净化

钢铁行业冷轧废水水质复杂、化学需氧量（COD）高，且Fe²⁺对COD去除干扰大。为了满足冷轧废水达标排放的要求，采用四室动态电渗析法，截留去除COD的同时，考察了Fe²⁺的去除效率，优化了操作参数。在动态实验中，用V-I曲线法测定系统的极限电压，分析了电压、浓度、流速和时间对COD和盐分去除率的影响。电渗析设备的阴极采用不锈钢板，阳极采用Ti/SnO₂-Sb/PbO₂,HMTECH-5010-1型均相阴、阳离子交换膜。最佳操作条件为：阴、阳极室进水流速为28.8 mL/min，淡化室和浓缩室流速为19.2 mL/min,12 V恒压输出，阴极室HCl的浓度为0.03 mol/L，阳极室NaOH的浓度为0.03 mol/L。在此操作条件下，淡化室出水pH约为3.0，废水中Fe²⁺的去除率98.5%（出水浓度<100 mg/L）,COD的去除率96.1%（出水<80 mg/L），出水水质符满足《钢铁工业水污染物排放标准》（GB 13456-2012）。     

复合膜电极对溶液中碘离子电化学离子分离性能

在多孔碳纤维毡基体上通过化学沉积法制备了具有电活性的聚吡咯复合膜电极,在两电极体系下对溶液中的碘离子进行电化学离子吸附分离操作,其中氧化状态下具有阴离子交换功能的聚吡咯复合膜电极作阳极。考察了不同操作电压、溶液pH值对膜电极分离性能的影响,并在混合溶液中考察了膜电极对碘离子选择性。结果表明,电压的适当升高与溶液pH值的降低有利于提高膜电极对碘离子的吸附速率和容量增高。复合膜电极表现出对碘离子优良的选择性吸附特性和可多次重复使用性。     

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     

Surface layer modification of AEMs by infiltration and photo‐cross‐linking to induce monovalent selectivity

Surface modification of anion exchange membranes (AEMs) by attaching a negatively charged layer is the main method for preparing monovalent anion selective membranes. However, tremendous increase of membrane resistance and poor long‐term stability of the modified membranes face great challenges. In this work, a photosensitive molecule (4,4‐diazostilbene‐2,2‐disulfonic acid disodium salt [DAS]) was infiltrated into the membrane surface and immobilized in the structure by cross‐linking under UV irradiation. This method introduced negative charge to the surface layer of the AEMs without increasing membrane thickness, leading to high performance membrane with high monovalent anion selectivity. The optimized membrane (D‐5) shows the highest perm‐selectivity of 11.21, which is superior to the commercial selective membrane Selemion^® ASV and previously reported monovalent anion selective AEMs. Furthermore, the newly developed membrane exhibits excellent long‐term stability, which can maintain constant selectivity during the 80 h ED experiment. © 2017 American Institute of Chemical Engineers AIChE J, 64: 993–1000, 2018     

Separation of mixed salts(Cl~-/SO_4~(2-)) by ED based on monovalent anion selective membranes

The industrial products or wastewater rich in the mixed salts(Cl~-/SO_4~(2-)) not only causes the environmental damage, but also induces waste of resource. In this study, an ED stack with monovalent selective AEMs and conventional CEMs was employed to separate the Cl~-and SO_4~(2-)from simulated wastewater. The effect of current density and mass fraction percentage was investigated in order to optimize the experimental conditions during ED process. It was found that at a concentration ratio between NaCl and Na_2SO_4 of 95/5(wt%/wt%) and a current density of40 m A·cm~(-2), a current efficiency of 72%, an energy consumption of 1.6 k W·h·kg~(-1) Na Cl and a Cl~-/SO_4~(2-)concentration(67.5/3.5 g·L~(-1)) were obtained. Hence, it is appropriate and effective to separate Cl~-and SO_4~(2-)by ED using the monovalent selective AEMs.     

Effect of interlayer anions on chromium removal using Mg–Al layered double hydroxides:Kinetic,equilibrium and thermodynamic studies

The influence of interlayer anions such as NO3-, SO42-and Cl-on Mg–Al hydrotalcites for Cr(VI) removal from aqueous solution was studied. The structure of the prepared LDHs was characterized by XRD, SEM, FTIR, TGA, BET surface area and p Hzpc. The sorbent ability and sorption mechanisms were also investigated. The LDHs exhibit high removal for Cr(VI), and the sorbed amount depends on the nature of interlayer anion, which decreased in the following order: NO3-N Cl-N SO42-. Nitrate-containing LDH reached a Cr(VI) sorption equilibrium within only 30 min. The effects of operating conditions, including initial concentration, solution p H, agitation time and sorbent amount have been studied in batch mode. The optimum conditions were observed at an initial concentration of 100 mg·L-1, p H = 6, agitation time of 60 min and a sorbent dose of 2 g·L-1. The equilibrium data were fitted to the Langmuir, Freundlich and Dubinin–Radushkevich isotherm models. The Langmuir model was found to sufficiently describe the sorption process, offering a maximum sorption capacity of 71.91 mg·g-1. The sorption kinetic follows pseudo-second-order reaction with high accuracy. Thermodynamic parameters suggested that the sorption process is spontaneous and endothermic in nature.     

Cu(II) complexes as receptor molecules for development of new chloride sensors

Highly sensitive and selective chloride polymeric membrane sensors are developed that employ Cu(II) complexes as anion carriers. Optimized membrane sensors showed a near-Nernstian response towards chloride anion over a wide concentration range of 2.5 × 10⁻⁵ to 1.0 × 10⁻¹ M and have micromolar level detection limits. These sensors have fast response time and work well in the pH range of 4.2-9.6. They exhibited enhanced potentiometric selectivity for chloride over other anions, including more lipophilic anions such as perchlorate, thiocyanate, nitrate, etc. Response characteristics (e.g. detection limit, linear range, response slope and selectivity) of these sensors remain essentially the same over a period of ∼5 months, reflecting remarkable stability.     

Phase Behavior of Sodium Dodecyl Sulfate-n-Butanol-Kerosene-Water Microemulsion System

Experiments were carried out to investigate the influences of cation from electrolytes and acidity/alkalinity on the phase behavior of sodium dodecyl sulfate-n-butanol-organics-water （with electrolytes） microemulsion sys-tem. The organics used is commercial kerosene. The volume ratio of water to organics is 1︰1. The results show that the type and valence of electrolyte cations are important factors influencing the microemulsion behavior. Biva-lent Ca2＋is more effective than monovalent K＋and Na＋for the formation of Winsor type III and II microemulsion. For electrolytes with the same monovalent cation Na＋, i.e. NaCl and Na2CO3, anions in the electrolyte have some effect. Bivalent anion 23CO - leads to a lower activity of cation Na＋than monovalent anion Cl-. NaOH （or KOH） behaves similar with NaCl （or KCl）. When HCl is used as electrolyte, its acidity plays an important role. Phase in-version of microemulsion from type III （or II） to type I is observed through precipitation of Ca2＋using Na2CO3, neutralization of HCl by NaOH, and addition of water to the system, which releases the oil from the microemulsion.     

Effect of monovalent anions on cationic Gemini micro-emulsion

Micro-emulsion usually consists of water, oil, surfactants and co-surfactants, and each component has an effect on the phase behavior and solubilization of the micro-emulsion. When the surfactant in the micro-emulsion system is quaternary ammonium cationic Gemini surfactant, the surfactant mainly combines with the anions in the salt. With the increase of salt concentration, the phase transformation of Winsor I → Winsor Ⅲ → Winsor Ⅱ occurred, but the optimum salinity and salt width are different because of the type of salt. The effects of 5 different kinds of monovalent anions, including C₆H₅SO₃^-, I^-, Br^-, NO₃^- and Cl^-, on the phase behavior and solubilization of quaternary ammonium cationic Gemini micro-emulsion are researched by Winsor phase diagram. It is found that the effects of organic anions C₆H₅SO₃^- and I^- on the phase behavior and solubilization of quaternary ammonium cationic Gemini micro-emulsion are most significant, and the effects of Br^-, NO₃^- and Cl^- are less significant. Meanwhile, when the optimum solubilization is achieved, the amount of sodium benzoate is the least, indicating that the organic anion has stronger self-organization behavior with quaternary ammonium cationic Gemini surfactants.     

用于混合一价盐分离的纳滤膜的制备及性能研究

针对有机颜料废水中单价相似离子（例如CH₃COO^-和Cl^-）分离难的问题,以表面活化能与脱水现象协同作用的分离机制为指导,在界面聚合中加入3,5-二氨基苯甲酸（DMA）来调控孔径、电性等性质,制备对醋酸根和氯离子具有高选择性的复合纳滤膜。XPS结果表明DMA参与界面聚合反应,形成疏松选择层;Zeta电位表明膜表面负电性增强。通过pH、操作压力等条件优化,得出0.6%（质量） DMA-TFC膜性能最佳,水通量较未改性复合膜提高44%,对于醋酸钠与硫酸钠的分离比达到15.0。本工作为相似离子分离纳滤膜的设计与制备提供了理论和实践基础,在颜料废水等水处理、物料分离等领域展现了良好的应用前景。     

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。     

Fabrication of anti-fouling polyamide nanofiltration membrane by incorporating streptomycin as a novel co-monomer

Polyamide (PA) thin-film composite (TFC) nanofiltration (NF) membrane has extremely broad application prospects in separation of monovalent/divalent inorganic salts mixed solution. However, membrane fouling is the main obstacle to the application of PA, TFC and NF membrane. Streptomycin (SM) is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups. In this work, the NF membrane was prepared via interfacial polymerization (IP) between trimesoyl chloride (TMC) in the organicphaseand SM/piperazine (PIP) mixture in theaqueousphase. The NF membrane structure and performance were characterized in detail. The results showed that SM successfully participated in the IP. The negative charge and hydrophilicity of membrane surface were improved. The prepared membrane exhibited good anti-adhesion and anti-bacterial performance. Additionally, when the SM concentration was 2%, the prepared membrane exhibited the optimal permselectivity. The water permeance was 89.4 L·m^-2·h^-1·MPa^-1. The rejection of NaCl and Na₂SO₄ were 17.17% and 97.84%, respectively. The NaCl/Na₂SO₄ separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^-1 NaCl and 1000 mg·L^-1 Na₂SO₄ mixed solution was 40, which was 3.3 times that of PIP/TMC membrane. It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance. This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.