摘要
双水相体系是近年来才迅速发展起来的一类新型萃取分离体系。它利用水溶性高聚物在无机盐存在下可以分成两相，被分离物质在两相中选择性分配的原理，使用特定的萃取方法，即可对所需物质进行分离。
本文利用聚乙二醇2000(PEG2000)—盐—H_2O双水相体系对同族(ⅣB族)元素钛(Ⅳ)和锆(Ⅳ)进行了分离富集研究。
(1) 研究了双水相体系的分相条件，以及无机盐、pH、高聚物的聚合度等因素对双水相体系的影响。
(2) 研究了以偶氮胂Ⅲ为萃取剂，钛(Ⅳ)和锆(Ⅳ)在双水相体系中的分配行为。通过大量实验，对影响萃取分离的酸度、萃取剂用量、盐用量、离子强度等诸多因素进行了分析。进行了不同配比的钛(Ⅳ)和锆(Ⅳ)的混合分离实验。
(3) 通过摩尔比法和连续变化法测定了PEG相中Zr(Ⅳ)与偶氮胂Ⅲ的络合组成。在9mol／L HCl中，Zr(Ⅳ)：ASAⅢ=1：2。根据吸收光谱分析了PEG相中钛(Ⅳ)离子与偶氮胂Ⅲ的作用关系，并考察了不同性质的表面活性剂对双水相体系中钛(Ⅳ)离子与偶氮胂Ⅲ萃取率的影响。根据实验结果，结合理论分析，探讨了该双水相体系中钛(Ⅳ)和锆(Ⅳ)的萃取机理。认为在PEG-盐-H_2O双水相体系中对金属离子的萃取是络合作用、静电引力、氢键、憎水键等多种力的综合结果。
(4) 在离子的测定方面，利用二安替比林甲烷和偶氮胂Ⅲ作显色剂，寻求出在PEG相中和盐水相中对钛(Ⅳ)和锆(Ⅳ)互不干扰的分光光度测定方法。分别对钛(Ⅳ)和锆(Ⅳ)进行分光光度测定。通过实验测定了络合体系的稳定时间和探讨了影响测定的一些因素，确定了最佳显色条件，充分利用该双水相体系的优点，不经反萃即可在上层PEG相中直接进行测定。
通过对钛(Ⅳ)和锆(Ⅳ)不同配比的混合分离实验。确定了最佳的分离条件。在pH=0.7，1.0m10.1％偶氮胂Ⅲ溶液，15m130％PEG溶液，体系总体积30ml，加入6g硫酸铵分相的条件下，成功的实现了钛(Ⅳ)和锆(Ⅳ)混合液的定量分离，98.4％Zr(Ⅳ)富集在PEG相中，而96％Ti(Ⅳ)富集在盐水相中。与以往传统的溶剂萃取法相比，具有分离率高、操作简便、价廉、无毒的优点。
Aqueous two-phase system is a new kind of extraction separation system quickly developed in recent years. Aqueous two-phase extraction is a technique which is used special extraction method and based the principle that soluble polymer solution can separate two phase in the presence of inorganic salt and matter will selective distribute in two phase.
The separation and concentration of two elements in the same group(IVB)-Titanium(IV) and Zirconium(IV) using polyethylene glycol 2000(PEG)-salt-water aqueous two-phase system were investigated.
(1) The conditions of PEG aqueous two-phase system separating into two phase and the factors affect extraction such as inorganic salt, pH, and the degree of polymerization of PEG were analyzed.
(2) The distribution behavior of Ti(IV) and Zr(IV) in aqueous two-phase system has been investigated in the presence of Arsenazo III as the extractant. The factors affect extractions such as pH, the concentration of extractant and salt, ionic strength, etc. were analyzed through many experiments. Ti(IV) and Zr(IV) were separated in mixing solution.
(3) The composition of Zr-ASAIII complex in PEG phase was determinated by mole ratio method and continuous variation method. Zr:ASAlII = l:2 in 9mol/L HC1. The relationship of Ti(IV) and Arsenazo III in PEG phase was analyzed through their absorption spectrum. The affection caused by different surface-active agents to the extractability was investigated. Mechanism of extraction in PEG aqueous two-phase system was studied on the basis of the results and combined theory. It was believed that metal extraction in Aqueous two-phase system is the result of complexation reaction, electrostatic effect and hydrogen bonding and hydrophobic bonding.
(4) In the ionic determination, the effective spectrophotometry to Ti(IV) and Zr(IV) without interference were found. Ti(IV)and Zr(IV) were determinated by spectrophotometry with diantipyrylmethane(DAM)and ArsenazoIII(ASAIII) as the chromogenic agents. The stable time of complexes and the fators that affect
determination were studied. The optimized conditions were decided through many
experiments that used the characteristic factor of aqueous two-phase system to determinate metal ion in upper phase without back extraction.
The author decided optimized condition that is 1.0ml0.1% ArsenazoIIIsolution, 15ml 30%PEG solution, pH=0.7, 6g ammoniumi 30ml total volume and used PEG aqueous two-phase system have succeeded in the quantitation separation of Ti(IV) and Zr(IV)mixing solution : 98.4% Zr(IV) enrichments in PEG phase and 96% Ti(IV) enrichments in under phase. The method has high extractability, simple operation, low price, without poison advantages compared with traditional methods.
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