硫酸铀酰印迹离子交换树脂的合成及识别特性研究

为进行稀溶液中铀的浓缩,以硫酸铀酰为模板、二乙基烯丙基胺为功能单体,在水中采用自组装分子印迹技术制备了硫酸铀酰印迹离子交换树脂.对树脂合成条件进行了优化,研究了pH值对吸附量的影响、分子印迹聚合物MIPs-4的等温吸附与吸附动力学、柱内吸附与淋洗曲线等树脂识别性能.结果表明:印迹树脂对硫酸铀酰的吸附性能比非印迹树脂好,可以在pH=1～6范围内应用,并在pH为2左右时吸附能力最强.MIPs-4树脂的吸附等温线为"优吸"型,吸附在约3h达到平衡.当C0=0.125mg·mL-1时,Kd=0.249L·g-1.吸附液ρ(U)=1.0 mg·mL-1、接触时间4min进行的柱内试验得出MIPs-4的穿透体积、穿透容量和饱和容量分别为柱内树脂的床体积(BV)的22倍、21.6 mg·mL-1和36.2 mg·mL-1.以0.05 mol·L-1 H2SO4 1.0 mol·L-1 NaCl为淋洗液时,淋洗体积仅4BV,流出液中最大铀浓度达到17.6 mg·mL-1.印迹树脂的吸附和解吸性能好,可应用于低浓度铀的浓缩及含铀废水的处理.     

Removal of Liquid and Solid Impurities from Uranyl Nitrate Hexahydrate Crystalline Particles in Crystal Purification Process

The purification behavior of uranyl nitrate hexahydrate (UNH) was investigated to evaluate the decontamination performance of liquid and solid impurities using a dissolver solution of mixed oxide (MOX) fuel in batch experiments. The UNH crystal recovered from the MOX fuel dissolver solution containing simulated fission products (FPs) was purified by a sweating and melt filtration process. Although the decontamination factors (DFs) of Pu, Cs, and Ba did not change in the sweating process, that of Eu increased with increases in temperature and time. These results indicate that liquid impurities such as Eu were effectively removed by the sweating method, but solid impurities such as Pu, Cs, and Ba were minimally affected in the batch experiments. On the other hand, the DF of Ba increased with 0.45 and 5.0 μ filters in the melt filtration process. Since Pu and Cs formed as Cs₂Pu(NO₃)₆ in the course of U crystallization and was accompanied with the UNH crystal, these behaviors were similar to each other. Although the DFs of Pu and Cs did not change with the 5.0 μ filter, it increased approximately twofold with the 0.45 μ filter. The particle size of Cs₂Pu(NO₃)₆ is relatively small and might pass through the 5.0 μ filter in the melt filtration process. The liquid impurities as Eu remained in the molten UNH crystal with some filters.     

Investigation on biosorption of V (III), Ti(IV), and U(VI) ions from a contaminated effluent by a newly isolated strain of Galdieria sulphuraria

ABSTRACT

Algal biomass has a great potential for cleaning metal pollutants from wastewaters. In the present study, biosorption of three metals i.e., vanadium, titanium, and uranium which are appeared in contaminated effluent during the uranium ore mines processing or in sludge resulting from pure UO₂ processing are investigated by a new strain of Galdieria sulphuraria, SBU-SH1 KY651246, which is isolated from a sulfur hot spring. The optimum biosorption situations and efficiency of isolated alga are investigated for each metal. Looking at the results, it can be concluded that G. sulphuraria SBU-SH1 is amenable to biosorption and has a favorable efficiency.     

New method in synthesis of nano uranyl(VI) Schiff base complexes: Characterization and electrochemical studies

This study presents a new method in synthesis of nano uranyl Schiff base complexes. In this method slow addition of dilute uranyl(VI) acetate solution to dilute Schiff base solution following the reflux for about 24 h, yields nano uranyl(VI) Schiff base complexes. Characterization of Schiff base ligands and nano uranyl complexes has been done using ¹H NMR, IR, UV–vis spectroscopy, elemental analysis. Schiff base ligands were synthesized by the condensation of one mole 3,4-diaminobenzophenone and two moles salicylaldehyde or substituted salicylaldehyde (3-OMe, 4-OMe, 5-OMe, 5-Br, 5-Cl). The electrochemical properties of the uranyl(IV) complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, according to the following trend: 5-MeO < H < 5-Br ≈ 5-Cl. Also the effect of the position of the substituted groups of Schiff base on the anodic potentials is as follows: 5-OMe < 3-OMe < 4-OMe.     

柠檬酸溶浸硬岩铀矿的浸出特征及铀形态研究

对硬岩铀矿开展柠檬酸溶浸试验。结果表明,0.1mol/L的柠檬酸浸出120h的铀浓度为208mg/L,浸出率达到41.2%,比稀硫酸(pH=2.0)浸出率(3.7%)高37.5个百分点,且酸碱平衡后,柠檬酸与铀矿的络合作用明显;柠檬酸铀酰结合Fe~(3+)的[FeUO_2OHCit]~+形态占比达到62.18%,为浸出液中的优势形态,对Fe~(3+)的亲和性有利于铀矿中U(Ⅳ)氧化溶浸;质谱还检测到[UO_2H_2Cit]~+、[UO_2H_2CitH_3Cit]~+、[UO_2H_2Cit(H_3Cit)_2]~+、[UO_2H_2CitH_2O]~+和[(UO_2H_2Cit)_2H_3Cit]~(2+)等形态;溶浸过程中CaCO_3饱和指数始终为负值,溶浸过程中CaCO_3处于未饱和状态,不易形成沉淀;柠檬酸溶浸硬岩铀矿可行。     

包含酰胺类萃取剂的微胶囊萃取铀酰离子

用制备的包覆酰胺类萃取剂的微胶囊研究了其在水溶液中对ＵＯ＾２＋２的萃取条件。并对反萃取及微胶囊的重复使用作了初步探讨。结果表明,微胶囊包覆萃取剂后,隔开了有机相和水相,可避免乳化及三相的产生。     

离子液体用于溶剂萃取铀酰离子的初步研究

初步研究了以咪唑类离子液体1-辛基-3-甲基咪唑六氟磷酸盐([C8mim][PF6])、1-丁基-3-甲基咪唑六氟磷酸盐([C4mim][PF6])和季胺类离子液体三辛基甲基氯化铵([N8881][Cl])为稀释剂,TBP为萃取剂,从硝酸介质中萃取铀酰离子。研究结果表明,铀的萃取分配比随水相初始硝酸浓度的增加而增加,季胺类离子液体略好于咪唑类离子液体,但都比对照稀释剂异辛烷差。研究了以碳酸胍为反萃剂的反萃条件。碳酸胍在实验条件下均能从这3种离子液体萃取体系中定量反萃铀酰离子,解决了用离子液体萃取铀酰离子中的反萃及离子液体的循环使用问题。     

磁性纳米材料处理含铀废水的研究进展

磁性纳米材料具有较强的化学稳定性、可再生回收、良好的吸附性能和易于分离等优点,在去除水溶液中的铀酰离子方面有广泛的应用前景。然而,磁性纳米材料也存在易团聚、易氧化等不足,通过表面修饰或改性等方法可改善其不足,提高其对废水中铀酰离子的去除能力,改善其吸附效果。本文通过总结近年来的相关研究资料,概括了磁性纳米材料的种类,归纳总结并比较了不同种类磁性纳米材料对含铀废水的去除能力及优势与不足,探讨了磁性纳米材料在含铀废水处理中的应用并对其机理进行了分析,阐述了磁性纳米材料去除溶液中铀酰离子的影响因素,简述了目前磁性纳米材料在处理含铀废水中有待解决的问题,并对其在分离放射性元素方面的应用前景进行了展望。     

硫掺杂ZnFe2O4/蒙脱石复合材料的铀酰吸附研究

为获得铀酰(UO2²⁺)吸附性能高的吸附剂,以蒙脱石(Montmorillonite,MMT)和铁酸盐(ZnFe₂O₄)为原材料与L-半胱氨酸通过水热反应制备了硫掺杂ZnFe₂O₄(S-ZnFe₂O₄)和ZnFe₂O₄/MMT(S-ZnFe₂O₄/MMT),采用XRD、FTIR和SEM对S-ZnFe₂O₄和S-ZnFe₂O₄/MMT进行了结构表征,研究了pH、接触时间和UO2²⁺初始质量浓度对UO2²⁺吸附效果的影响,结果表明:S-ZnFe₂O₄呈高分散的纳米颗粒状,并且均匀分布于蒙脱石片层结构表面;S-ZnFe₂O₄与蒙脱石复合后能明显提高其UO2²⁺吸附性能,最佳吸附pH为6.0;S-ZnFe₂O₄和S-ZnFe₂O₄/MMT复合材料对UO2²⁺的最大吸附量分别为51.44 mg/g和68.45 mg/g;吸附符合Langmuir等温吸附模型和伪二阶动力学模型,说明吸附过程属于表面单分子层化学吸附。