Molecular modification of a novel macroporous silica-based impregnated polymeric composite by tri-n-butyl phosphate and its application in the adsorption for some metals contained in a typical simulated HLLW.
Molecular modification of a novel macroporous silica-based impregnated polymeric composite by tri-n-butyl phosphate and its application in the adsorption for some metals contained in a typical simulated HLLW.
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DOI：
10.1016/j.jhazmat.2007.01.056
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发表时间：
2007-08
影响因子：
13.6
通讯作者：
A. Zhang;Chengliang Xiao;E. Kuraoka;M. Kumagai
中科院分区：
文献类型：
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作者：
A. Zhang;Chengliang Xiao;E. Kuraoka;M. Kumagai
以三正丁基磷酸（TBP）为分子改性剂，合成了一种新型大孔硅基4,4′，（5′）-二（叔丁基环己酸）-18-冠-6 （DtBuCH18C6）聚合物复合材料（DtBuCH18C6+TBP/ SiO2-P）。采用先进的真空吸附技术，将dbuch18c6和TBP分子浸渍固定在SiO2-P颗粒的孔隙中。在298K下，考察了接触时间和hno3浓度（0.1 ~ 5.0 m）对(DtBuCH18C6+TBP)/ SiO2-P吸附的影响，研究了10种裂变和非裂变产物Sr（II）、Ba（II）、Ru（III）、Mo（VI）、Na(I)、K(I)、Pd（II）、La（III）、Cs(I)和Y（III）在（DtBuCH18C6+TBP）上的吸附。结果表明，在最佳浓度为2.0M HNO3(DtBuCH18C6+TBP)/ SiO2-P时，除Ba（II）外，其余元素对Sr（II）均表现出较强的吸附能力和较高的选择性。此外，在2.0M HNO3 （326.2ppm）中，(DtBuCH18C6+TBP)/ SiO2-P中DtBuCH18C6的泄漏量明显低于DtBuCH18C6/ SiO2-P中658.4ppm的泄漏量。这归因于dbuch18c6与TBP通过分子间相互作用，即氢键有效结合。用TBP对dbuch18c6进行分子修饰，显著降低了泄漏量。将(DtBuCH18C6+TBP)/ SiO2-P聚合物复合材料应用于MAREC工艺中高放废液（HLLW）中主要发热源Sr（II）的色谱分划，具有重要意义。
Using tri-n-butyl phosphate (TBP) as a molecular modifier, a novel macroporous silica-based 4,4′,(5′)-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) polymeric composite (DtBuCH18C6+TBP/SiO2–P) was synthesized. It was done by impregnating and immobilizing DtBuCH18C6 and TBP molecules into the pores of SiO2–P particles utilizing an advanced vacuum sucking technique. The adsorption of 10 fission and non-fission products Sr(II), Ba(II), Ru(III), Mo(VI), Na(I), K(I), Pd(II), La(III), Cs(I), and Y(III) onto (DtBuCH18C6+TBP)/SiO2–P was investigated by examining the influence of contact time and the HNO3concentration in a range of 0.1–5.0M at 298K. It was found that at the optimum concentration of 2.0M HNO3(DtBuCH18C6+TBP)/SiO2–P exhibited strong adsorption ability and high selectivity for Sr(II) over all of the tested elements, which showed very weak or almost no adsorption except Ba(II). Moreover, the quantity of DtBuCH18C6 leaked from (DtBuCH18C6+TBP)/SiO2–P in 2.0M HNO3, 326.2ppm, was obviously lower than 658.4ppm that leaked from DtBuCH18C6/SiO2–P. This was ascribed to the effective association of DtBuCH18C6 and TBP through intermolecular interaction, i.e., hydrogen bonding. The significant reduction of DtBuCH18C6 leakage by molecular modification with TBP was achieved. It was of great benefit to application of the (DtBuCH18C6+TBP)/SiO2–P polymeric composite in chromatographic partitioning of Sr(II), one of the main heat generators, from high level liquid waste (HLLW) in reprocessing of nuclear spent fuel in MAREC process developed recently.