Simultaneous separation and recovery of Cs(I) and Sr(II) using a hybrid macrocyclic compounds loaded adsorbent. Kinetic,equilibrium and dynamic adsorption studies

In this study, simultaneous separation and recovery of Cs(I) and Sr(II) from nitric acid solution was investigated using a silica-based hybrid adsorbent. The adsorbent was prepared by successive impregnation and fixing of two supramolecular recognition agents namely, 1,3-[(2,4-diethylheptylethoxy)oxy]-2,4-crown-6-Calix[4]-arene(Calix[4]arene-R14) and 4',4' (5")-di(tert-butylcyclohexano)-18-crown-6, onto a silica-based polymer support(SiO₂-P). Uptake properties, characterization, equilibrium kinetics, and dynamic adsorption properties of Cs(I) and Sr(II) were then assessed. Distribution coefficients (K_d) higher than 10² cm³/g for Cs(I) and Sr(II) were obtained using 3 M HNO₃ at 298 K, and the K_d values decreased with increasing temperature. Adsorption kinetics and equilibrium studies fitted well with pseudo-second-order model and Redlich–Peterson isotherm model, respectively. The constant total organic carbon values in the aqueous phase were obtained after adding 10^?3 ～ 4 M HNO₃. Results of the dynamic adsorption/elution test indicated that Cs(I) and Sr(II) were efficiently and simultaneously captured and eluted even under a flow rate of 1.5 cm³/min.     

Calcium isotope separation by band chromatography using 18-crown-6-ether resin

To develop the ⁴⁸Ca enrichment process, a feasibility study on a band chromatography was made using 9 M HCl solution and crown ether resin synthesized in porous silica beads. Prior to the chromatographic experiments, distribution coefficients, Kd, of Ca²⁺ and Sr²⁺ were measured at different concentrations of these ionic species. The frontal boundary of the chromatography was made by a usual manner of the breakthrough mode of calcium feeding, and the rear boundary was made by introducing strontium as a following ion on the basis of the observed Kd values. It was confirmed that the heavy isotope ⁴⁸Ca was depleted in the rear boundary region, while ⁴⁸Ca was enriched in the front boundary region. The values of separation coefficient ε (= α – 1) in three chromatographic operations at different temperatures were observed as 2 × 10^?3 ~ 3 × 10^?3. The separation coefficients observed in the front boundary regions, where ⁴⁸Ca was enriched, agreed with those observed in the rear boundary regions, where ⁴⁰Ca was enriched.     

18-冠-6/LA/Fe3O4复合磁性纳米粒子的制备及其吸附性能研究

Fe₃O₄磁性纳米粒子（MNPs）比表面积大、吸附能力强,且在外磁场作用下易于液固分离,冠醚具有对铀酰离子选择性配位的能力。本研究制备了兼具两者特点和优势的18-冠-6/LA/Fe₃O₄复合磁性纳米粒子。其结构经红外（IR）、扫描电镜-X射线能谱（SEX/EDX）、振动样品磁强计（VSM）、热综合分析仪（TGA）进行表征,表明18-冠-6/LA/Fe₃O₄复合磁性纳米粒子的粒径为12～23 nm,饱和磁化强度为56.34 emu/g。用制得的复合磁性纳米粒子对溶液中铀酰离子进行初步吸附实验,在选定的条件下,平衡吸附率达95%,操作方法快速简便,吸附后的磁粒子可方便地进行富集和回收。     

新型冠醚-膦酸锆材料的制备及其对锶吸附性能研究

为高效分离锶元素,本文采用直接反应插层的方法将4-氨基苯并-18-冠-6引入α相磷酸锆层间获得新型冠醚@膦酸锆复合材料（D-AM-ZrP）。通过控制反应过程中无机磷与有机膦的比例获得具有花状形貌及有序结构的D-AM-ZrP。该材料可有效的结合α-ZrP与4-氨基苯并-18-冠-6的优势,在复杂体系中对Sr²⁺具有良好的吸附性和选择性,在弱酸性条件下对Sr²⁺的吸附容量达到136.42 mg·g^-1,优于未插层的α-ZrP(28.17 mg·g^-1)。     

冠醚包覆聚苯乙烯磁性颗粒的合成、表征及其对锶离子的吸附性能

为建立应用磁性颗粒快速分离低水平~(90)Sr的方法,分别以沉淀法合成Fe_3O_4纳米颗粒,微乳聚合法合成磁性聚苯乙烯-二乙烯苯颗粒(Pst-DVB@Fe_3O_4),并将4,4’(5’)-二叔丁基二环己基-18-冠-6(DtBuCH18C6)通过物理作用包覆在Pst-DVB@Fe_3O_4颗粒表面,最终生成一种新型的核-壳结构的DtBuCH18C6包覆的聚合物磁性颗粒(DtBuCH18C6@Pst-DVB@Fe_3O_4)。采用扫描电镜、红外光谱、X射线光电子能谱等方法对颗粒的形貌、结构、表面元素组成及含量进行分析。用于分离水溶液中Sr~(2+)的批实验结果表明,Sr~(2+)的吸附量随着pH值而增加,而在pH=11和pH=13之间急剧上升,温度升高,其吸附量增加。吸附动力学模型结果表明,Sr~(2+)在DtBuCH18C6@Pst-DVB@Fe_3O_4表面的吸附更接近于其和Sr~(2+)之间形成络合物的单层化学吸附过程,符合Langmuir模型。在优化的条件下其最大吸附容量为2.62 mg/g。     

Influence of Gamma-Irradiation on Extraction and Cation-Transport of Uranium(VI) and Plutonium(IV) by Dicyclohexano-18-Crown-6

Changes of the extraction behaviour and cation-transport of U (VI) and Pu (IV) nitrates with r-irradiated DC18C6 in toluene have been investigated. The effect of radiation damage to DC18C6 for extraction and permeation at excessively higher doses (70 Mrads) has been studied systematically. No deterioration in its performance is noted at lower doses. Hydrolytic stability of the macrocycle/diluent system in the presence of nitric acid and radiolytic stability of immobilized liquid membrane using ‘Enka’ Accurel flat sheet polypropylene membrane films as solid support are also examined.     

A novel chromatographic separation technique using tertiary pyridine resin for the partitioning of trivalent actinides and lanthanides

A novel chromatographic separation technique using a tertiary pyridine type resin has been applied to the partitioning of the trivalent actinides (An) and lanthanides (Ln) and several successful results have been shown. In an alcoholic hydrochloric acid system, the trivalent An were clearly separated from the Ln, while no such group separation was achieved in an alcoholic nitric acid system. On the other hand, the nitric acid system was more effective for the intragroup (i.e. individual) separation of the trivalent An and the Ln than the hydrochloric acid system. On the basis of these results, a novel concept for the partitioning of the trivalent An and Ln using the present separation technique and its flowchart have been proposed with its advantages and disadvantages.     

Development of a simple reprocessing process using selective precipitant for uranylions — Engineering studies on systems for precipitating and separating

The simple reprocessing method based on precipitation using N-cyclohexyl-2- pyrrolidone (NCP) as a selective precipitant for U and Pu ions from dissolved solutions of spent FBR fuels has been developed. On the basis of fundamental studies on precipitation behaviors, we designed and built up the scaled-up laboratory equipments (1/20-scale of future plant capacity of 200 tHM/y) to evaluate technological and economical feasibility. This system, which mainly consists of a precipitator and a precipitate separator, should be operated continuously from economical reasons. From the experimental results, it was confirmed that the precipitator is capable of producing UO₂²⁺-NCP precipitate stably with stipulated residence time (approximately 30 min), and the precipitate separator has the highly efficient separation of precipitate from the slurry. Furthermore, the parametric experiments indicated that the rinsing operation increased the efficiency in decontamination of FP elements.