Waste acid recovery utilizing monovalent cation permselective membranes through selective electrodialysis

Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a potential difference.However,the current SED process is limited by conventional commercial monovalent cation permselective membranes(MCPMs).This study systematically investigates the use of an independently developed MCPM in the SED process for acid recovery.Various factors such as current density,volume ratio,initial ion concentration,and waste acid systems are considered.The independently developed MCPM offers several advantages over the commercial monovalent selective cation-exchange membrane(CIMS),including higher recovered acid concentration,better ion flux ratio,improved acid recovery efficiency,increased recovered acid purity,and higher current efficiency.The SED process with the MCPM achieves a recovered acid of 95.9%and a concentration of 2.3 mol·L^(–1) in the HCl/FeCl_(2) system,when a current density of 20 mA·cm^(-2) and a volume ratio of 1:2 are applied.Similarly,in the H_(2)SO_(4)/FeSO_(4) system,a purity of over 99%and a concentration of 2.1 mol·L^(–1) can be achieved in the recovered acid.This study thoroughly examines the impact of operation conditions on acid recovery performance in the SED process.The independently developed MCPM demonstrates outstanding acid recovery performance,highlighting its potential for future commercial utilization.

Monovalent cation perm-selective membranes(MCPMs)"New developments and perspectives

As one of the most typical and promising membrane processes, electrodialysis(ED) technique plays a more and more significant role in industrial separation. Especially, the separation of monovalent cations and multivalent cations is currently a hot topic, which is not only desirable for many industries but also challenging for academic explorations. The main aim of the present contribution is to view the advances of a wide variety of monovalent cation perm-selective membranes(MCPMs) and their preparation technologies including(1) covalent crosslinking,(2) surface modification,(3) polymer blending,(4) electrospinning,(5) nanofiltration alike membrane,and(6) organic–inorganic hybrid. The relevant advantages and disadvantages with respect to some specific cases have been discussed and compared in detail. Furthermore, we elaborately discuss the opportunities and challenges of MCPMs, the fabricating strategies to take and the future perspectives.

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 C_6H_5SO_3^-, I-, Br-, NO_3^- 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 C_6H_5SO_3-and I-on the phase behavior and solubilization of quaternary ammonium cationic Gemini micro-emulsion are most significant, and the effects of Br-, NO_3^- 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.

Separation of mixed salts(Cl-/SO42-) by ED based on monovalent anion selective membranes

The industrial products or wastewater rich in the mixed salts(Cl-/SO4^2-) 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 SO42-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 Na2SO4 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-/SO4^2-concentration(67.5/3.5 g·L^-1) were obtained. Hence, it is appropriate and effective to separate Cl-and SO42-by ED using the monovalent selective AEMs.

Synthesis, Crystal Structure and Characterization of Energetic Monovalent Copper Azide Complex: [Cu_2(dmpz)(N_3)_2]_n

A novel cuprous azide complex with the formula of [Cu2（dmpz）（N3）2]n（1, dmpz： 2,6-dimethylpyrazine） has been synthesized through hydrothermal synthesis with the reducibility of H3PO3 and structurally characterized by single-crystal X-ray diffraction method. Single-crystal X-ray diffraction analysis reveals the title complex represents a three-dimensional network structure featuring 2D [Cu N3]n plane units bridged by bridging dmpz ligands to form a 3D network. Research results reveal that 1 has lower impact sensitivity and friction sensitivity, which may be expected to become insensitive energetic material and have potential applications. Crystal data： monoclinic, space group C2/c, a = 17.8599（15）, b = 8.2889（5）, c = 14.8076（14） A, β = 113.2580（10）o, V = 2014.0（3） A3, Z = 8, S = 1.025, the final R = 0.0303, w R = 0.0825 for 1460 observed reflections with I 2σ（I） and R = 0.0386, wR = 0.0870 for all reflections. In addition, elemental analysis, IR, and sensitivity characterization are presented.

Influence of monovalent cations and CuO nanoparticles on X-nanozeolite in uranium anionic species separation from contaminated drinking water

The main purpose of this work was the modification of NaX nanozeolite using copper oxide nanoparticles and various monovalent cations such as K^+, Cs^+, and Ag^+in order to make the negatively charged zeolite surface accessible for anionic forms of uranium which are the most dominant species of uranium in the contaminated radioactive waters at natural p H. Various methods such as the X-ray fluorescence(XRF), X-ray powder diffraction(XRD), field emission scanning electron microscopy(FE-SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FT-IR), and atomic absorption spectroscopy(AAS) were used to characterize the final synthesized absorbents. Batch technique was used to study the adsorption behavior of uranium ions from polluted drinking water by Na X nanozeolite and its modified forms. In order to better understand the performance of them, the results were compared with those that were obtained for synthesizing bulk NaX zeolite and Na-form of clinoptilolite natural zeolite. Preliminary results indicated that uranium sorption increased as the loading level of CuO nanoparticles on NaX nanozeolite increased from 2.1 wt% to 11.2 wt%. In addition,from the obtained data, an increase in uranium removal efficiency resulted as charge/ionic radius ratio of exchanged cation decreased. Also, the effect of contact time, solid–liquid ratio, initial concentration and temperature on the adsorption process was studied. It is worth mentioning that, in this study, the sorption of uranium was performed under natural conditions of pH and the presence of competing cations and anions which are available in drinking waters.

SELECTION OF NEW EPITOPES FROM MONOVALENT DISPLAYED PHAGE OCTAPEPTIDE LIBRARY

A library of 2 ×107 random octapeptides was constructed by use of phagemid-based monovalent phage display system. The randomly synthesized degenerated oligodeoxyribonucleotides (oligos ) were fused to the truncated g Ⅲ (p230-p403). Sequence analysis of 11 randomly chosen clones suggested that the degenerated inserts and its deduced amino acid (aa) sequences are randomly distributed. The library was used to select binding peptides to the monoclonal antibody (mAb) 9E10, which recognizes a continuous decapeptide epi- tope of denatured human c-myc protein. After four to five rounds of panning, most of the eluted clones could bind to 9E10. Sequence analysis of the selected positive clones indicated that the binding sequences could fall into two classes, one class (clone 1) shares a consensus motif, ISE x x L, with c-myc decapeptide; and the sequences of the other class are entirely different. The binding of both classes to 9E10 could be specifically inhibited by free c-myc decapeptide. The immunogenicity of the phage peptide was further investigated by construction of multivalent displayed phage peptides and immunization of animals with or without adjuvant. ELISA and competitive ELISA showed that anti-serum from both mice and rabbit immunized with either clone could bind to the original antigen, c-myc decapeptide. These results denote that in spite of the dissimilarity of the selected peptides with c-myc decapeptide, they are capable of inducing similar immune respones in vivo, thus actually mimicking the antigen epitope.

膜法分离一/二价阳离子的研究进展

各类工业过程如水质软化、食用盐纯化、盐湖卤水提锂、酸和重金属资源回收等对一/二价阳离子高效分离的需求日益增长,近年来,针对上述分离体系的膜材料的研究取得了诸多进展。本文详细总结了针对一/二价阳离子分离的选择性阳离子交换膜、纳滤膜、支撑液膜和离子印迹膜的研究进展,重点梳理了相关膜材料的离子选择性优化思路和机理,对比分析了上述膜过程的特点和适用场景。基于此,作者认为,离子筛分精细化是膜分离技术的重要发展方向。在分子尺度明晰分离层的形成和演化机理,对于提高界面聚合反应可控度,实现在亚纳米尺度膜结构的精细调控至关重要。通过在膜基体内可控构建目标离子的特异性识别位点和传质通道,有望实现高选择性离子筛分。此外,具有本征规则孔道结构的新型分离膜材料,如MOFs、COFs、二维层状结构膜等,在精细筛分方面具有良好的发展潜力。

单价选择性电渗析回收铅酸蓄电池拆解废酸试验

研究针对北方某铅酸蓄电池回收厂拆解废铅酸蓄电池车间的拆解废酸进行单价选择性电渗析回收试验,并考察了操作电流密度、电压及流量对单价选择性电渗析工艺的影响,以期为铅酸蓄电池回收工业清洁生产提供技术支撑。在电压为5 V,电流密度为20 mA/cm^(2),进水流量为150 L/h,电渗析装置运行时间为48 min的条件下,回收室中H^(+)透过率可达到80%,单价选择性电渗析对H^(+)有较高透过率。同时,单价选择性电渗析对金属离子保持较低的泄漏率,Pb^(2+)泄漏率为0.6%,Zn^(2+)泄漏率为2.8%,Cd^(2+)泄漏率为1.8%。研究实现了对废铅酸蓄电池拆解废酸中H+与重金属离子的选择性分离的目标。

基于构式词法的领属复合词界定

以往研究根据成分间有无领属关系判定领属复合词,忽略了形式和整体的作用,混淆了潜在的、蕴含的和实现的领属关系,导致领属复合词与属性复合词界限不清。构式词法将复合词看成整体、独立的形式—意义对。据此,领属复合词中的领属关系必须是实现的,对应领属结构。构式视角下的领属复合词有命名功能但无分类功能,中心成分是一价的,有不可让渡的领属关系。判断一个词是否是领属复合词,要看它能否识解为该词法构式的构例,关键是有无分类功能。根据构式标准,本文调整了领属复合词的范围,使之边界更清晰,内部更统一,与领属短语更平行,更符合认知。两种复合词界限有些模糊是因为有些中心成分介于一价与零价之间。

镁合金负差数效应的研究进展

随着我国工业水平的不断进步,工程应用领域对轻量化的需求愈加迫切,极大推动了镁合金的快速发展。然而,镁合金的耐蚀性较差,严重阻碍了其实际工程应用。为了有效解决镁合金耐蚀性差的问题,亟需深入研究其腐蚀机理。镁合金电化学腐蚀过程中存在典型的负差数效应(Negative difference effect,NDE),即在阳极极化下镁合金的析氢速度随电位升高而增加,与传统的电化学动力学理论相异。近年来,国内外学者对镁合金的负差数效应开展了大量研究,先后建立了局部保护膜模型、单价镁离子模型、溶解脱落模型、氢化镁促溶理论、综合理论、部分电子外电路消耗机理、析氢交换电流密度i0增大机理和电催化机理八种理论模型。基于上述模型,人们深化了对镁合金析氢过程的认识,提升了镁合金腐蚀机理的研究深度。本文综述了镁合金电化学腐蚀过程中负差数效应的基本原理及研究现状,归纳出八种负差数效应的理论模型,总结了各模型的发展历程,指出了它们各自存在的不足之处,展望了镁合金腐蚀负差数效应的研究方向。

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。

Fe^(3+)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Fe^(3+)引入阳离子交换膜,并利用电场作用和Fe^(3+)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Fe^(3+)浓度对改性膜性能的影响。表明随着Fe^(3+)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Fe^(3+)对多巴胺聚合过程的共同影响,当Fe^(3+)的浓度为0.001mol/L时,改性膜Na^(+)/Mg^(2+)选择性高达12.8,并且具有较低的膜电阻和优异的稳定性。

单价选择性离子交换膜的制备方法

单价选择性离子交换膜在硬水软化、杂盐纯化、盐湖提锂等领域具有重要作用。通过总结一、二价离子选择透过膜的制备方法,解释了膜表面修饰改性和掺混改性这两种改性方法的原理和特点及其标志性案例。研究发现,采用表面涂覆、电沉积、化学接枝等方法可有效提高离子交换膜对一、二价离子的选择分离性能,对实际应用具有较大的参考意义。

一价/二价阳离子浓度对蛋白质-核酸液液相分离的调控

蛋白质和核酸的液液相分离(liquid-liquid phase separation,LLPS)对无膜细胞器的形成起着重要作用.在病理研究中,LLPS也可以导致蛋白质的异常聚集从而引起某些神经退行性疾病的发生.因此研究蛋白质-核酸LLPS的有效调控,能够对理解生物结构功能以及相关疾病治疗提供一定的参考价值.主要利用光学显微镜、动态光散射仪以及紫外分光光度计,研究一价/二价阳离子对多聚赖氨酸(poly-L-lysine,PLL)-脱氧核糖核酸(DNA)LLPS的调控,并对其机制进行分析.试验中观察到PLL-DNA的LLPS会随着钠/钾离子浓度的升高而逐渐形成沉淀,从出现沉淀到沉淀最多时,钠/钾离子浓度大约为100 mmol/L到600 mmol/L.在钠离子浓度高于600 mmol/L时聚合物沉淀开始溶解,再次有LLPS发生.然而镁/钙离子对于PLL-DNA的聚合物的调控表现出更高的效率,形成沉淀的镁/钙离子临界浓度为50 mmol/L,重新发生LLPS的浓度大约为300 mmol/L.通过对该溶液的吸光度进行分析,得到的结论与显微镜观察一致,并且该溶液的电泳迁移率随着一价/二价阳离子浓度的升高出现了逆转现象,即电泳值由负变正,说明一价/二价阳离子对蛋白质-核酸LLPS的调控与电荷变化有关,二价阳离子对其调控效率高于一价阳离子.最后,绘制了一种聚合物的结构模型,并为这一相分离过程提供合理的解释.

煤化工浓盐水电渗析浓缩过程中一、二价离子选择性规律研究

基于实验室电渗析系统,研究了高盐浓度下不同初始离子质量比物料的迁移规律及其对一、二价离子选择性的影响。结果表明,当初始氯化钠(NaCl)与硫酸钠(Na_(2)SO_(4))的质量比≥3∶1时,电渗析在浓缩过程中表现出明显的分盐效果,而当其质量比≤3∶5时,电渗析在浓缩过程中脱盐液侧可以实现Na_(2)SO_(4)的纯化;当初始NaCl与Na_(2)SO_(4)的质量比≥2∶5时,氯离子具有优先迁移性,而当初始NaCl与Na_(2)SO_(4)的质量比为1∶5时,硫酸根离子开始具有优先迁移性。

离子分离用电荷Janus结构单价选择性阳离子交换膜

单价选择性阳离子交换膜(M-CEMs)已被广泛应用于环境修复和能量收集等领域,例如,从卤水和海水中提取Na^(+)或Li^(+)。然而,由于膜结构和材料的限制,M-CEMs存在渗透选择性低的问题。在此,我们提出了一种简单的方法以构建具有电荷Janus结构的新型M-CEMs,该结构由荷正电的均苯三甲酸/聚乙烯亚胺选择层和荷负电的商业阳离子交换膜(CEM)组成。选择性电渗析(SED)分析结果表明,具有电荷Janus结构的M-CEMs可以有效抑制多孔阳离子交换膜中存在的阴离子迁移问题,因而使这种具有电荷Janus结构的M-CEMs具有较高的渗透选择性和总阳离子通量。与最先进的单价选择性阳离子交换膜的分离性能相比,具有电荷Janus结构的M-CEMs对于Na^(+)/Mg^(2+)的最高渗透选择性可以达到145.77,这超过了目前单价选择性阳离子交换膜性能的“上限”,且对于Li^(+)/Mg^(2+)也具有优异的渗透选择性(14.11),在离子分离领域具有巨大的应用潜力。这项研究可以为具有电荷Janus结构的M-CEMs的设计提供新的见解,并应用于不同的环境和能源领域。

P-mSA/mCS双极膜的制备及其在一价、二价离子分离中的应用

以五氧化二磷、磷酸三乙酯和磷酸为反应剂,制备了磷酸化海藻酸钠(P-SA),经二茂铁离子改性后作为阳膜层(P-mSA);用乙酰基二茂铁改性壳聚糖制备了阴膜溶胶(mCS).将阴膜溶胶流延于阳膜层上,制备了P-二茂铁-SA/乙酰基二茂铁-CS双极膜(P-mSA/mCS BPM).测定了双极膜的红外光谱、接触角、电荷密度、离子交换容量与交流阻抗.IR与接触角的分析结果表明,SA经磷酸化后,亲水性能得到了显著提高.将P-mSA/mCS BPM应用于一价、二价离子的分离,当压力差为0.3MPa时,二价离子的截留率(双极膜截留的离子百分数)为95%,一价离子的截留率为22%左右.

单价选择性阳离子交换膜的研究进展

总结了国内外单价选择性阳离子交换膜的发展历史,探讨了单价阳离子交换膜的制备方法,重点比较了电沉积表面改性、光化学反应表面改性和浸渍法改性法的优缺点,并进一步分析了单价选择性阳离子交换膜存在的限制因素和其广阔的应用前景.

ZnO压敏陶瓷的一价离子掺杂

本文研究了一价金属离子掺杂对ＺｎＯ压敏陶瓷电性能的影响。根据晶界的双Ｓｃｈｏｔｋｙ势垒模型分析计算了ＺｎＯ晶柱表层１５ｎｍ浅范围的正电荷中心浓度ＮＤ对ＺｎＯ压敏陶瓷小电流区非线性特性的影响。结果表明ＮＤ减小，非线性增强。如果掺入ＺｎＯ压敏陶瓷中的一价金属离子进入了ＺｎＯ晶粒体内对正电中心进行补偿。