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Uranium, plutonium and neptunium co-recovery with high nitric acid concentration in extraction section by simplified solvent extraction process 采用简化溶剂萃取法在萃取段高硝酸浓度条件下对铀、钚和镎进行共回收
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1671
M. Nakahara, Y. Sano
Abstract As a part of NEXT, the behavior of Np in a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery was investigated. Two approaches to Np co-recovery with U and Pu in the irradiated fast reactor core fuel using a dissolver solution in a counter current were examined. One used a feed solution with a high HNO3 concentration, and the other used a scrubbing solution with a high HNO3 concentration. The leakages of Np to the raffinate were 1.1 and 4.7% using high HNO3 concentration feed and scrubbing solutions, respectively. Simulation results based on these experiments showed that high HNO3 concentration in the feed solution is advantageous for the Np extraction because Np oxidation progresses in the feed solution before being supplied into the centrifugal contactor, and there is less effect of HNO2 at the extraction section.
摘要:作为NEXT的一部分,研究了以TBP为萃取剂的简化溶剂萃取工艺中Np的行为,该工艺用于U、Pu和Np的共回收。研究了两种利用逆流溶解溶液与辐照快堆堆芯燃料中的铀、铀共回收Np的方法。一种使用高HNO3浓度的进料溶液,另一种使用高HNO3浓度的洗涤溶液。在高HNO3浓度进料和洗涤液中,Np对萃余液的泄漏量分别为1.1%和4.7%。基于上述实验的模拟结果表明,高HNO3浓度的进料液有利于Np的提取,因为在进料液进入离心接触器之前,Np已经在进料液中进行了氧化,而HNO2在提取段的影响较小。
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引用次数: 7
Extraction of americium(III) from nitric acid medium by CMPO-TBP extractants in ionic liquid diluent 离子液体稀释剂中cpo - tbp萃取剂萃取硝酸介质中的镅(III)
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1975
A. Rout, K. Venkatesan, T. Srinivasan, P. Vasudeva Rao
Abstract Extraction of americium(III) from nitric acid medium by a solution of tri-n-butylphosphate (TBP) and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (bmimNTf2), was studied and the results were compared with that obtained with CMPO-TBP in n-doddecane (n-DD). The distribution ratio of 241Am(III) in TBP-CMPO/bmimNTf2 was measured as a function of various parameters such as concentrations of nitric acid, CMPO, bmimNO3, NaNO3 and TBP and temperature. Remarkably large distribution ratios were observed for the extraction of americium(III) when bmimNTf2 acted as diluent and the extraction was insignificant in the absence of CMPO. The stoichiometry of metal–solvate in organic phase was determined by the slope analysis of extraction data and it indicated the formation of 1:3 (Am:CMPO) complex in organic phase. Viscosity of TBP-CMPO/bmimNTf2 at various temperatures and enthalpy change accompanied by the extraction of americium(III) were determined and reported in this paper.
摘要研究了在室温离子液体1-丁基-3-甲基咪唑双(三氟甲烷磺酰基)亚胺(bmimNTf2)中,用三正丁基磷酸丁酯(TBP)和正辛基(苯基)-N, n-二异丁基氨基甲酰甲基氧化膦(CMPO)溶液从硝酸介质中萃取镅(III),并与正十二烷(n-DD)中CMPO-TBP的萃取结果进行了比较。测定了241Am(III)在TBP-CMPO/bmimNTf2中的分布比例与硝酸、CMPO、bmimNO3、NaNO3和TBP浓度以及温度的关系。以bmimNTf2作为稀释液时,镅(III)的提取分布比明显增大,而在没有CMPO的情况下,提取效果不显著。通过萃取数据的斜率分析确定了有机相中金属溶剂化物的化学计量,表明有机相中形成了1:3 (Am:CMPO)配合物。本文测定并报道了TBP-CMPO/bmimNTf2在不同温度下的粘度和萃取镅(III)时的焓变。
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引用次数: 45
Determination of 126Sn half-life from ICP-MS and gamma spectrometry measurements ICP-MS和γ能谱法测定126Sn半衰期
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1673
P. Bienvenu, L. Ferreux, G. Andreoletti, N. Arnal, M. Lépy, M. Bé
Abstract A new value of 126Sn half-life was determined by combination of inductively coupled plasma-mass spectrometry (ICP-MS) and gamma spectrometry measurements on purified sample solutions collected from nuclear fuel reprocessing. 126Sn was isolated through dissolution of fission product precipitates and liquid-liquid extraction with N-benzoyl-N-phenyl-hydroxylamine (BPHA). The abundance of 126Sn atoms together with the absence of interfering species in the analysed solutions made it possible to measure both mass concentration and nuclide activity with high precision and accuracy. This led to a 126Sn half-life value of 1.980(57)×105 a.
摘要采用电感耦合等离子体质谱法(ICP-MS)和伽马谱法对核燃料后处理的纯化样品溶液测定了新的126Sn半衰期。126Sn通过裂变产物沉淀溶解和n -苯甲酰- n -苯基-羟胺(BPHA)液液萃取分离得到。在分析的溶液中,126Sn原子的丰度以及干扰物质的缺失使得测量质量浓度和核素活性具有很高的精度和准确性。这导致126Sn的半衰期值为1.980(57)×105 a。
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引用次数: 15
Evaluation of trace elements in chewing tobacco and snuff using instrumental neutron activation analysis (INAA) and atomic absorption spectroscopy (AAS) 中子活化分析和原子吸收光谱法评价嚼烟和鼻烟中微量元素
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1672
S. Waheed, N. Siddique, S. Rahman
Abstract Nine samples of chewing tobacco, snuff, tobacco leaf and ash were analyzed using Instrumental Neutron Activation Analysis (INAA) and Atomic Absorption Spectroscopy (AAS). Almost all samples of chewing tobacco and snuff studied in this work contain substantial amounts of Mg, Mn, Na, K, V, Sc, Rb and Fe. Furthermore, varying amounts of Al, Ba, Ca, Ce, Co and Zn were also detected in all tobacco samples. Of the toxic elements which were determined using INAA, As, Sb and Hg were quantified in only few tobacco samples. However, other toxic elements, which were determined using AAS, such as Cu, Pb and Cd were detected in almost all samples of chewing tobacco and snuff. The concentration of majority of the detected elements is high in ash samples which imply that most elements in chewing tobacco and snuff may originate from the addition of ash.
摘要采用仪器中子活化分析(INAA)和原子吸收光谱(AAS)对9种烟草样品进行了分析。本研究中几乎所有的咀嚼烟草和鼻烟样品都含有大量的Mg、Mn、Na、K、V、Sc、Rb和Fe。此外,在所有烟草样品中还检测到不同数量的Al、Ba、Ca、Ce、Co和Zn。在INAA法测定的有毒元素中,砷、锑和汞仅在少数烟草样品中被定量。然而,在几乎所有的咀嚼烟草和鼻烟样品中都检测到其他有毒元素,如Cu、Pb和Cd,这些元素是用原子吸收光谱法测定的。烟灰样品中检测到的大多数元素的浓度都很高,这意味着咀嚼烟草和鼻烟中的大多数元素可能来自烟灰的添加。
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引用次数: 1
X-ray absorption spectroscopic study of trivalent and tetravalent actinides in solution at varying pH values 不同pH值溶液中三价和四价锕系元素的x射线吸收光谱研究
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1674
B. Brendebach, N. Banik, C. Marquardt, J. Rothe, M. Denecke, H. Geckeis
Abstract We perform X-ray absorption spectroscopy (XAS) investigations to monitor the stabilization of redox sensitive trivalent and tetravalent actinide ions in solution at acidic conditions in a pH range from 0 to 3 after treatment with holding reductants, hydroxylamine hydrochloride (NH2OHHCl) and Rongalite (sodium hydroxymethanesulfinate, CH3NaO3S). X-ray absorption near edge structure (XANES) measurements clearly demonstrate the stability of the actinide species for several hours under the given experimental conditions. Hence, structural parameters can be accurately derived by extended X-ray absorption fine structure (EXAFS) investigations. The coordination structure of oxygen atoms belonging to water ligands surrounding the actinide ions does not change with increasing pH value (approximately 11 O atoms at 2.42 Å in the case of U(IV) at pH 1, 9 O atoms at 2.52 Å for Np(III) at pH 1.5, and 10 O atoms at 2.49 Å for Pu(III) up to pH 3), indicating that hydrolysis reactions are suppressed under the given chemical conditions.
摘要采用x射线吸收光谱(XAS)研究了在pH范围为0 ~ 3的酸性条件下,盐酸羟胺(NH2OHHCl)和熔铝酸盐(羟甲磺酸钠,CH3NaO3S)处理后,氧化还原敏感的三价和四价锕系离子在酸性条件下的稳定性。在给定的实验条件下,x射线吸收近边结构(XANES)测量清楚地证明了锕系元素在几个小时内的稳定性。因此,通过扩展x射线吸收精细结构(EXAFS)研究可以准确地推导出结构参数。锕系离子周围属于水配体的氧原子的配位结构不随pH值的增加而改变(pH值为1时,U(IV)的配位结构约为11个O原子在2.42 Å, pH值为1.5时,Np(III)的配位结构约为9个O原子在2.52 Å, pH值为3时,Pu(III)的配位结构约为10个O原子在2.49 Å),表明在给定的化学条件下水解反应受到抑制。
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引用次数: 51
Novel polymer vectors of 64Cu 新型64Cu聚合物载体
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1669
J. Kozempel, M. Hrubý, M. Nováková, J. Kučka, L. Lešetický, O. Lebeda
Abstract We describe a preparation of novel polymer vectors of 64Cu based on co-polymers of poly- (N-isopropylacrylamide) and poly- (N-hydroxypropylmethacrylamide). DOTA, DTPA, dipicolylamine, thiosemicarbazone and Ag-ionophore-II ligands were tested to bind 64Cu in a polymer chain. Labeling yields with no-carrier-added 64Cu varied from 95 to 99% in 30 min. at laboratory temperature. Vectors were stable in vitro for 24 h in human serum and might be prospective for targeted 64Cu radio or combined radiochemotherapy.
摘要以聚n -异丙基丙烯酰胺和聚n -羟丙基甲基丙烯酰胺为共聚物,制备了新型64Cu载体。测试了DOTA、DTPA、二聚胺、硫代氨基脲和ag - ionophotor - ii配体对64Cu在聚合物链上的结合作用。在实验室温度下,无载流子添加64Cu的标记收率在30分钟内从95%到99%不等。载体在人血清中稳定存在24 h,有望用于靶向64Cu放化疗或放化疗联合应用。
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引用次数: 2
An adapted purification procedure to improve the quality of 90Y for clinical use 一种改进的纯化程序,以提高临床使用90Y的质量
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1666
Abmel Xiques Castillo, Keila Isaac Olivé, Edgar Casanova González, Denis Beckford, R. Leyva Montaña, A. Montero Álvarez, Eunice Olivé Álvarez
Abstract There is an increasing interest for 90Y for radionuclide therapy. However, radioimmunotherapy, one of the most important applications for 90Y, demands a very high purity product. Obtaining a high quality 90Y is difficult not only because of the complex and time consuming production schemes but also because of the quality control which has challenging tasks like the determination of 90Sr at very low concentrations. The present paper investigates a reported purification procedure for the removal of stable metal trace contaminants from an 90Y solution, seeking for its potential use in the elimination of the radioactive contaminant 90Sr and its fast determination. For this purpose a washing step with HNO3 acid is introduced to elute 90Sr, the order of each acid solution is rearranged to reduce the potential contaminants present in acids and the size of the column is reduced to further optimize the procedure. As a result, an improved purification method is obtained, which allows the removal of both trace metal contaminants and 90Sr from an 90Y solution and the measurement of 90Sr/90Y ratios of the order of 10-7, which are well below the established pharmacopeia limit of 2×10-5.
放射性核素治疗对90Y的兴趣越来越大。然而,放射免疫治疗是90Y最重要的应用之一,需要非常高的纯度产品。获得高质量的90Y是困难的,不仅因为生产方案复杂且耗时,而且因为质量控制具有挑战性的任务,如在极低浓度下测定90Sr。本文研究了一种从90Y溶液中去除稳定金属痕量污染物的净化程序,寻求其在消除放射性污染物90Sr及其快速测定中的潜在用途。为此,引入HNO3酸洗涤步骤来洗脱90Sr,重新排列每个酸溶液的顺序以减少酸中存在的潜在污染物,并减小色谱柱的尺寸以进一步优化程序。结果,获得了一种改进的纯化方法,该方法允许从90Y溶液中去除痕量金属污染物和90Sr,并测量90Sr/90Y的10-7量级的比率,远低于既定药典限值2×10-5。
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引用次数: 12
Kinetic and thermodynamic studies on the adsorption of U(VI) ions on densely crosslinked poly(methacrylic acid) from aqueous solutions 密交联聚甲基丙烯酸吸附U(VI)离子的动力学和热力学研究
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1668
C. Özeroğlu, G. Keçeli
Abstract In this study, densely crosslinked poly(methacrylic acid) was used to adsorb uranium(VI) ions from aqueous solution. For this purpose, the crosslinked copolymer of ethylene glycol dimethacrylate (EGDM) and methacrylic acid (MA) containing 25% (w/w) methacrylic acid (MA) was synthesized by using dibenzoyl peroxide-N,N-dimethylaniline (BPO-DMA) initiator system at room temperature. The adsorption of uranium(VI) ions on the copolymer sample (0.02 g copolymer/5 mL solution of U(VI) ions) was carried out in a batch reactor. The parameters which effect the uranium adsorption process, such as, contact time, pH of solution, initial uranium(VI) concentration and temperature were investigated. It was observed that an increase in these parameters enhanced the removal of U(VI) ions from aqueous solution. The adsorption data were modelled by the Freundlich, Langmuir and Dubinin–Radushkevich (D–R) isotherms. The adsorption capacity of the crosslinked copolymer and free energy change were calculated by using D–R isotherms. Thermodynamic parameters (ΔH°, ΔS° and ΔG°) were determined for the adsorption of U(VI) ions from aqueous solutions by the crosslinked copolymer bearing methacrylic acid functional groups. Experimental adsorption data were analyzed using sorption kinetic models of the pseudo-first order and pseudo-second order kinetic models. It was observed that pseudo-second order kinetic model provided a high goodness of fit with experimental data for the adsorption of U(VI) ions on the crosslinked copolymer bearing methacrylic acid functional groups. The densely crosslinked poly(methacrylic acid) might be of interest in large scale uranium removals from aqueous solution, since it had high uranyl sorption capacities ranging from 0.16 mmol/g to 2.37 mmol/g copolymer at pH 2.7 (293 K).
摘要采用密交联聚甲基丙烯酸吸附水溶液中的铀(VI)离子。为此,采用过氧化二苯甲酰- n, n -二甲苯胺(BPO-DMA)引发剂体系,在室温下合成了含25% (w/w)甲基丙烯酸(MA)的乙二醇二甲基丙烯酸酯(EGDM)与甲基丙烯酸(MA)交联共聚物。在间歇反应器中进行了铀(VI)离子在共聚物样品(0.02 g共聚物/5 mL U(VI)离子溶液)上的吸附。考察了接触时间、溶液pH、初始铀浓度和温度等参数对铀吸附过程的影响。结果表明,这些参数的增加对U(VI)离子的去除率提高。吸附数据采用Freundlich、Langmuir和Dubinin-Radushkevich (D-R)等温线建模。用D-R等温线计算了交联共聚物的吸附量和自由能变化。测定了含甲基丙烯酸官能团的交联共聚物从水溶液中吸附U(VI)离子的热力学参数(ΔH°,ΔS°和ΔG°)。采用拟一级和拟二级吸附动力学模型对实验吸附数据进行了分析。结果表明,含甲基丙烯酸官能团的交联共聚物吸附U(VI)离子的拟二级动力学模型与实验数据拟合度较高。密交联聚(甲基丙烯酸)可能对从水溶液中大规模去除铀感兴趣,因为它在pH 2.7 (293 K)下具有高的铀酰吸附能力,范围为0.16 mmol/g至2.37 mmol/g共聚物。
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引用次数: 18
Production and separation of no-carrier-added 93,94,95Tc from 9Be activated yttrium target 9Be活化钇靶中无载体添加93,94,95tc的制备与分离
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1667
M. Maiti, S. Lahiri
Abstract Proton rich Tc radionuclides have been produced for the first time through 89Y(9Be, xn)93,94,95Tc reactions. In order to optimize the yield of a particular radionuclide of choice, batch yield of 93Tc, 94Tc and 95Tc have been measured at different incident energies using stacked-foil technique followed by off-line γ-spectrometry. No-carrier-added (nca) 93,94,95Tc radionuclides have been separated from bulk yttrium by liquid–liquid extraction (LLX) and solid–liquid extraction (SLX) techniques. Trioctylamine (TOA) diluted in cyclohexane was used as liquid anion exchanger in LLX in presence of HCl. SLX was carried out using cation and anion exchanger resin, DOWEX-50 and DOWEX-1, respectively, in HCl medium.
摘要通过89Y(9Be, xn) 93,94,95tc反应首次制备了富质子Tc放射性核素。为了优化所选放射性核素的产率,采用叠片技术和离线γ能谱法测量了不同入射能量下93Tc、94Tc和95Tc的批产率。采用液-液萃取(LLX)和固-液萃取(SLX)技术从大块钇中分离出无载流子(nca) 93,94,95tc放射性核素。用环己烷稀释的三辛胺(TOA)作为液体阴离子交换剂,在HCl存在下在LLX溶液中进行交换。SLX分别使用阳离子交换树脂DOWEX-50和阴离子交换树脂DOWEX-1在HCl介质中进行。
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引用次数: 6
Determination of solubility parameters of cobalt(II) and indium(III) oxinates by tracer technique 示踪法测定氧化钴(II)和氧化铟(III)的溶解度参数
Pub Date : 2009-12-01 DOI: 10.1524/RACT.2009.1665
M. Mandal, R. Sarkar (Sain), S. Basu
Abstract Effects of different diluents on the extraction of cobalt(II) and indium(III) oxinate complexes have been studied using Co-60 and In-114m as radiotracers. Theory of regular solutions was applied for the determination of solubility parameters (δ) of cobalt oxinate and indium oxinate which were found to be 34.45 J1/2cm-3/2 and 34.03 J1/2 cm-3/2, respectively. Besides, distribution of each of the two complexes was studied in the mixtures of two solvents, assigned as good and poor solvents, in accordance with their individual behaviors. In both of the two cases, experimentally determined values of distribution-coefficient differed from those of calculated values which shows the importance of solute-solvent and solvent-solvent interaction in the present system.
以Co-60和In-114m为示踪剂,研究了不同稀释剂对氧化钴(II)和氧化铟(III)配合物萃取的影响。用正溶液理论测定了氧化钴和氧化铟的溶解度参数δ,分别为34.45 J1/2cm-3/2和34.03 J1/2cm-3/2。此外,研究了这两种配合物在两种溶剂的混合物中的分布,根据它们各自的行为,将它们分为好溶剂和坏溶剂。在这两种情况下,分配系数的实验测定值与计算值不同,这表明了溶剂-溶剂和溶剂-溶剂相互作用在当前体系中的重要性。
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引用次数: 0
期刊
Radiochimica Acta Radiochimica Acta
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