从铜熔炼烟灰浸出液中萃取分离铜的试验研究

以铜熔炼烟灰浸出液为研究对象，采用N902萃取剂从中分离回收铜，并将铜元素进行富集。研究了萃取剂浓度、相比(O/A)、溶液pH值、振荡时间对铜萃取分离的影响，以及反萃剂浓度、相比、振荡时间对铜反萃率的影响。试验结果表明，在萃取剂质量分数12%、相比(O)/(A)=1∶2、溶液pH值为2.0、振荡时间6 min的萃取条件下，通过两级逆流萃取，铜、锌、铁的萃取率分别为98.26%、1.29%、2.28%;铜与铁、锌的分离系数分别达到4346和2425,实现了铜与铁、锌的有效分离。在选定反萃剂硫酸铜浓度为2.5 mol/L、相比(O)/(A)=2∶1、振荡时间6 min的条件下，通过两级逆流反萃，铜的反萃率为94.68%,反萃后铜质量浓度达到7.04 g/L,相较于浸出液中铜离子质量浓度提高了约3.72倍，实现了铜离子的富集，得到的硫酸铜溶液可用于电积铜生产。     

湿法炼锌中性浸出液中铜、镉的萃取分离无渣净化工艺

用ＡｃｏｒｇａＭ５６４０萃取剂对硫酸锌浸出液优先萃取分离铜．用二（２－乙基己基）二硫代磷酸（Ｄ２ＥＨＤＴＰＡ）和三辛胺（ＴＯＡ）协萃体系进行锌、镉分离．应用Ｄ２ＥＨＤＴＰＡ－甲苯体系时,镉完全萃取,但有机相中的镉很难反萃．应用Ｄ２ＥＨＤＴＰＡ－ＴＯＡ协萃体系时,镉能从硫酸锌溶液中选择性萃取,也能很容易地从有机相中反萃,实现镉与锌的分离．提出了从硫酸锌中性浸出液萃取分离铜、镉的无渣净化新工艺．     

用二(2-乙基己基)二硫代磷酸-三辛胺协萃体系分离锌和镉

分别应用二（2-乙基己基）二硫代磷酸（D2EHDTPA）和D2EHDTPA-三辛胺（TOA）协萃体系进行了锌、镉分离的研究。D2EHDTPA萃取锌和镉的等摩尔系列法、红外光谱、核磁共振的测试结果表明,萃合物的组成可能为CdA_2和ZnA_2。应用D2EHDTPA-甲苯体系时,镉容易完全萃取,但有机相中的镉很难反萃下来。应用D2EHDTPA和TOA组成的协萃体系时,镉能从硫酸锌溶液中选择性萃取,也能很容易地从有机相中反萃下来,实现镉与锌的分离。萃取速度的控制步骤是界面反应。     

叔胺萃取分离钴(Ⅱ)、铁(Ⅱ)

研究了不必预先氧化二价铁,直接用叔胺从氯化物溶液中萃取分离钴(Ⅱ)、铁(Ⅱ)的新方法.考察了不同改性剂对叔胺萃取钴(Ⅱ)、铁(Ⅱ)的影响以及各种因素对钴(Ⅱ)、铁(Ⅱ)萃取、洗涤及反萃的影响.提出了用叔胺萃取分离钴(Ⅱ)、铁(Ⅱ)的最佳工艺参数.     

HPMαFP与1,10-菲罗啉(Phen)等中性萃取剂对Co(Ⅱ)协同萃取的性能研究

对在氯仿溶液中用1－苯基－3－甲基－4－（α-呋喃甲酰基）吡唑啉酮）－5（HPMαFP）对Co（Ⅱ）的萃取性能进行了研究。结果表明，HPMαFP萃取效果随其浓度的增大而显著增加，还研究了HPMαFP与1，10－菲罗啉（Phen)、三辛基氧膦（TOPO）、二苯亚砜（DPSO），2，2′－联吡啶（DIPY）的氯仿溶液对Co(Ⅱ）的协同萃取，结果是HPMαFP与Phen的协萃作用显著，与DIPY协萃作用较小，与TOPO、DPSO无协萃效应；还根据模拟萃合物Co（PMαFP）2和Co(PMαFP）.Phen的红外光谱和元素分析结果，讨论了萃合物的结构。     

提高钛白废酸提钪萃取选择性的研究

研究旨在选择合适的助萃剂LH,提高二（2-乙基己基）磷酸（P204）-磷酸三丁酯（TBP）-磺化煤油体系对钛白废酸提钪的选择性,提高钪钛分离系数和钪铁分离系数。研究采用的工艺为二次萃取富集、二次反萃成钪、化学精制提纯钪。通过正交试验确定最佳萃取工艺条件：萃取剂最佳配比V（P204）∶V（TBP）∶V（磺化煤油）=1.3∶0.7∶10,一次萃取相比为V（O）∶V（A）=1∶21,不加助萃剂二次萃取相比为V（O）∶V（A）=1∶5,加助萃剂时其加量为水相体积的1.7%,此时钪钛分离系数达到124 812,钪铁分离系数达到8 202。     

二茂铁异羟肟酸过渡金属（Ⅱ）螯合物的合成与表征

用二茂铁异羟肟酸和Ｎ－苯基二茂铁异羟肟酸为配体，分别与锰（Ⅱ）、铁（Ⅱ）、钴（Ⅱ）、镍（Ⅱ）、铜（Ⅱ）、锌（Ⅱ）的氯化物或醋酸盐反应，合成了１０种新的螯合物。通过元素分析、红外光谱和核磁共振氢谱确认了螯合物的结构。     

季铵盐萃取草酸的机理

季铵盐可以直接从氰化浸出液中萃取金，但反萃困难. 酸性硫脲通空气体系能有效反萃季铵盐中的氰化金，向反萃液中添加草酸可以显著提高金的反萃效率. 实验发现在反萃过程中，草酸会被萃取进入有机相. 本文通过3个萃取模型分别拟合草酸的萃取反应并用红外光谱法研究了萃取机理，结果表明，季铵盐萃取草酸的机理主要为中性缔合，草酸的COOH基团与季铵盐的极性端作用，形成1:1型氢键萃合物，表观平衡常数2.12，还有少部分草酸以失去一个氢离子的二聚体形式与Cl–发生阴离子交换，与季铵阳离子形成1:2型离子对萃合物，表观平衡常数0.0031.     

羧烷基-季铵两性壳聚糖的制备及其阻垢杀菌性能

采用氯乙酸、丙烯酸和2,3-环氧丙基三甲基氯化铵对壳聚糖（CTS）改性,制得羧甲基-季铵壳聚糖（CMQAC）和羧乙基-季铵壳聚糖（CEQAC）,并通过IR、1H NMR、XRD对产物进行了结构确证。用静态阻垢的方法对两性壳聚糖衍生物阻硫酸钙垢的性能进行了评价,结果表明两性壳聚糖用量为16 mg/L、[Ca2＋]〈2000 mg/L、[SO42-]〈4800 mg/L时,阻垢率可达到100%。用小瓶测试法测定不同季铵取代度（DS）的两性壳聚糖对异养菌的杀菌效果。研究结果表明,在用量为30 mg/L时,CMQAC季铵取代度为0.73时杀菌率为99.7%,CEQAC季铵取代度为0.50时杀菌率为99.2%,改性后壳聚糖衍生物的阻垢和杀菌性能与壳聚糖相比有了明显提高。     

LK-C2萃取分离废线路板酸浸液中的铁和镍

针对废线路板酸浸液的硝酸介质体系,探讨了用LK-C2分离铁（Ⅲ）和镍的萃取及反萃条件。pH值为3.00和10.00时分步采用20%LK-C2-煤油二级逆流萃取铁（Ⅲ）和镍,萃取率分别为96.14%和99.35%。分别采用2.00 mol/LHCl二级逆流反萃回收铁和3.00 mol/LH₂SO₄三级逆流反萃回收镍,反萃率分别为99.18%和98.32%。     

季胺萃取锌的动力学研究

以恒界面池法研究了氯化物介质中季胺萃锌的动力学。考查了搅拌转速、传质界面积和温度对萃取速率的影响，判定季爱萃锌为界面化学反应的动力学模式。进一步研究了季胺萃取剂浓度和水相Ｚｎ＾２＋浓度对萃取速率的影响，得到了与理论推断相吻合的速率方程。     

Extraction of Benzene and Naphthalene Carboxylic Acids Using Quaternary Ammonium Salts As a Model Study for the Separation of Coal Oxidation Products

Abstract

The ion‐pair solvent extraction of benzene‐ and naphthalene‐carboxylic acids has been investigated as a model study for the separation of coal oxidation products, which are formed by treatment with alkaline solutions at high temperatures. It was possible that benzene‐ and naphthalene‐dicarboxylic acids are extracted into several types of organic solvents with quaternary ammonium ions. The extraction equilibrium constants (K_ex) for benzoic acid, 1,2‐benzenedicarboxylic acid, 1,3‐benzenedicarboxylic acid, 1‐naphthoic acid, 2‐naphthoic acid, 2,3‐naphthalenedicarboxylic acid, and 2,6‐naphthalenedicarboxylic acid into chloroform were determined at 20°C. The difference of K_ex among the aromatic acids was sufficiently large for designing a separation method for these aromatic acids. It was unexpected that the extraction of dicarboxylic acids was slower than that of monocarboxylic acids, although the ion‐pair formation of aromatic carboxylate ion with quaternary ammonium ion is normally considered as a diffusion control reaction in aqueous phase. Thus, this fact suggests that the phase transfer of the ion‐pair from aqueous to organic phase is the rate‐determining step. Liner‐free‐energy relationship was observed for the monocarboxylic acids using different quaternary ammonium salts while that was ambiguous for the dicarboxylic acids. This is due to the steric influence of the counter ions for the magnitude of K_ex.     

3-氨基-4-吡唑甲酸乙酯金属配合物的合成

农药由于毒性太强对人体危害比较大。近年来,研究发现农药中间体与金属化合物络合生成的金属配合物可以延长农药半衰期,降低对哺乳动物的毒性,提高其生物药效,为寻找绿色农药提供了依据。以农药中间体3-氨基-4-吡唑甲酸乙酯为主要研究对象,分别和氯化铜、氯化锌、氯化钡、硫酸亚铁铵4种金属化合物反应,合成4种新的金属配合物,采用红外光谱,核磁氢谱和单晶数据对合成的金属配合物进行分析。     

盐酸介质中锌缓蚀剂的研制和评价

利用失重法研究了盐酸溶液中各类缓蚀剂对锌的缓蚀作用.结果表明,在盐酸介质中对锌起缓蚀作用的化合物主要是有机物,但缓蚀率不佳.实验发现,在0.8 mol/L的盐酸溶液中丙炔醇、碘化钾和季铵盐的协同作用对锌具有很强的缓蚀作用,并对缓蚀剂在不同浓度、不同温度条件下的缓蚀效果进行比较,得出缓蚀剂最佳配比和最佳使用条件.     

CTMAB插层有机膨润土的结构分析

通过X射线衍射(X-ray)、差(DTA)和热重(TG)等手段分析了不同工艺条件下制备的十六烷基三甲基溴化铵(CTMAB)插层有机膨润土(CTMAB-MMT),讨论了有机膨润土的结构和层间发生的有机化反应,确定了本实验的最佳工艺条件,首次提出了季铵盐在插层过程中分解出季铵离子头的观点.初步认为不仅体积较大的有机阳离子可以插入蒙脱石片层间,体积较小的有机阳离子也可以插入其中.     

Separation of Cobalt and Nickel by Liquid Surfactant Membranes Containing a Synthesized Cationic Surfactant

ABSTRACT

Separation of cobalt(II) and nickel(II) by using a hydroxyoxime extractant has been investigated both in liquid-liquid extraction and in a liquid surfactant membrane(LSM) system. In the liquid-liquid equilibrium extraction studies, hydroxyoximes showed significant extractability for nickel ions, although LIX 84 was found to have exceptional chelating affinity for nickel ions. In the LSM system functionalized by hydroxyoxime, the cobalt ions were efficiently separated from nickel ions as a result of slower permeation of nickel chelates across the emulsion membrane. More complete cobalt recovery was achieved in the LSMs dosed with LIX 860 than when the same carrier was applied to the liquid-liquid extraction system. Furthermore, cobalt permeation rate was enhanced threefold when a quaternary ammonium type of cationic surfactant was used as an emulsifier due to carrier interaction with surfactant at the reaction interface. The permeation mechanism of ions in LSMs was elucidated by an interfacial reaction model which took into account the adsorption of the carrier and surfactant at the reaction interface.     

Hydration counteracts the separation of lanthanides by solvent extraction

The extraction of lanthanides from aqueous nitrate solutions by quaternary ammonium nitrate ionic liquids (e.g., [A336][NO₃]) shows a negative sequence (i.e., light lanthanides are more efficiently extracted than heavy lanthanides), which conflicts with the lanthanide contraction. In this study, we explored the origin of the negative sequence by investigating the extraction of lanthanides from ethylammonium nitrate by [A336][NO₃]. The extraction shows a positive sequence, which is converted to a negative sequence with the addition of water. The transformation from positive to negative sequences reveals that the negative sequence is caused by the hydration of lanthanide ions: hydration of lanthanide ions counteracts the extraction. Therefore, the use of solvents that have weak solvation with lanthanide ions might enhance the separation of the elements by solvent extraction.     

The effect of different ammonium structure of quaternary ammonium resin on the electrochemical properties

The quaternary ammonium resin is synthesized by the ring-opening reaction of an epoxy resin with a tertiary amine in the presence of a proton donor in the solution. This kind of resin can be dispersed in the water phase to form a conductible milky dispersion. In this study, different kinds of tertiary amines including the full-alkyl group and the ester group-containing or urethane group containing tertiary amine are reacted with DGEBA-type epoxy resin to synthesize the quaternary ammonium resins. The resin characteristics and the electrochemical properties of its emulsion are investigated. In addition, properties of the emulsion prepared from tertiary amine salt resin are also measured for comparison. It is found that if the substituted groups of the ammonium structure of the quaternary ammonium resin are all alkyl groups, rupture voltage of the emulsion is very low. But when one of the substituted group contains an ester group or an urethane group, rupture voltage increases remarkably and the resin can be used for electrodeposition. Meanwhile, the electrodeposition theory of quaternary ammonium resin and its thermal cross-linking reaction and the electrochemical properties of coemulsion prepared by mixing the quaternary ammonium resin and the tertiary amine salt resin are also discussed. © 1993 John Wiley & Sons, Inc.     

Ion aggregation in the polysiloxane ionomers bearing pendant quaternary ammonium groups

Polysiloxane ionomers bearing pendant quaternary ammonium groups were synthesized through the Menshutkin reaction of poly(γ‐chloropropylmethylsiloxane‐co‐dimethylsiloxane) with N,N‐dimethylbenzylamine. Ion aggregation in the ionomers with different contents of the quaternary ammonium groups was investigated by torsion braid analysis, transmission electron microscopy, and rheological measurements. It was found that the incorporation of the quaternary ammonium groups did not make a significant effect on the glass transition temperature of the polysiloxane matrix. The glass transition of the cluster phase was found in the range of ?20–40°C, depending on the concentration of the ion pair. The cluster phase was visualized under TEM when the concentration of the quaternary ammonium group exceeded a critical value. It was indicated by rheological data that the movement of polymer chains in the cluster phase of the polysiloxane ionomers was not restricted at the room temperature, which might be related to the weaker interaction between the bulky quaternary ammonium ion pairs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3099–3104, 2002; DOI 10.1002/app.10009     

Synergistic Solvent Extraction and Separation of Lanthanide(III) Ions with 4‐Benzoyl‐3‐Phenyl‐5‐Isoxazolone and the Quaternary Ammonium Salt

The solvent extraction of the lanthanide(III) ions (without Pm) with a 4‐benzoyl‐3‐phenyl‐5‐isoxazolone(HPBI) alone and in the presence of the quaternary ammonium salt Aliquat 336 in perchlorate form (QClO₄) in C₆H₆ was investigated by the slope analysis method. The composition of the extracted species was determined as Ln(PBI)₃ and Q[Ln(PBI)₄] (Q⁺ is the quaternary ammonium salt cation). The values of the equilibrium constant were calculated. Synergistic effects were found for all lanthanide metals when they were extracted with a binary mixture of HPBI and QClO₄. The influence of the synergistic agent on the extraction process has been discussed. The parameters of the extraction process were determined. The separation factors between adjacent metals were evaluated.