单一还原剂氨基羟基脲净化PUREX流程铀纯化循环中的钌

钌是重要的裂变产物之一,在核燃料后处理的铀纯化循环中通过预处理工艺改变钌的化学形态可改进钌的净化效果。采用氨基羟基脲(HSC)作为预处理工艺中的还原剂,研究还原剂浓度、预处理酸度、预处理温度等因素对钌的预处理效果的影响,并进行铀纯化循环萃取净化工艺的台架试验验证。结果表明：氨基羟基脲作为预处理试剂对提高铀纯化循环中钌的净化系数具有明显作用;在铀纯化循环台架温试验中钌的净化系数为1 455,在PUREX流程中具有良好的应用前景。     

单甲基肼预处理对2D槽中钌的净化研究

通过单级条件实验研究单甲基肼或肼浓度、预处理酸度、温度等因素对钌预处理效果的影响。采用确定的条件进行了模拟铀纯化循环2D槽的串级实验，获得了1CU料液经单甲基肼预处理后钌的净化系数（DF（Ru））。串级结果列于表1。结果表明，单甲基肼作为预处理试剂提高钌净化的效果明显，较料液中未加预处理试剂的净化系数提高近8倍。     

Purex流程中酸度对锆钌净化的影响

在保证Purex流程中钌高净化效率的基础上,尽量提高锆的去污效率,以优化 Purex流程去污工艺.本文通过搭建台架试验平台,采用多级萃取方式,模拟Purex流程中共去污过程,开展了 1 AF酸度和 1 AS酸度对铀锆钌在流程中的分布情况及对锆钌去污效果的影响研究.研究结果表明:提高1 AF酸度不利于锆的去污,有利于钌的...     

单甲基肼改善铀纯化循环中钌的净化

通过单级条件实验研究单甲基肼或肼浓度、预处理酸度、温度等因素对钌的预处理效果的影响。采用确定的条件进行了模拟铀纯化循环2D槽的串级实验,获得了料液经单甲基肼或肼预处理后钌的净化系数（DF_Ru）。结果表明,单甲基肼作为预处理试剂提高钌净化的效果明显,与料液中未加预处理试剂相比,其净化系数提高近10倍,且在相同预处理条件下,其预处理效果优于肼。通过台架温试验,进一步验证了单甲基肼对钌的预处理效果,钌的净化系数达到10⁴。     

乙异羟肟酸预处理对钌的净化行为研究

本工作研究了乙异羟肟酸（AHA）浓度、酸度、温度及时间等因素预处理对钌（Ru）净化的影响。结果表明，提高AHA浓度、降低预处理酸度，Ru的分配系数（D（Ru））降低，有利于对Ru的净化；提高预处理温度，延长预处理时间，D（Ru）值降低，预处理效果明显。     

高放玻璃固化尾气中净化钌的滤材筛选

高放废液玻璃固化过程中,钌是最容易挥发的元素,给尾气处理带来困难。文章收集了大量的过滤材料,经初步筛选,选定为KSG-1抗爆硅胶和W-X-14三氧化二铁,并分别测定了过滤柱的温度、滤材装填高度、气流速度、滤材的捕集量以及NO_2,SO_2气体等对钌的过滤效率的影响。结果表明KSG-1(温度120℃),W-X-14(温度500℃)对钌的去污因数均≥1×10~4。净化效果是令人满意的。     

单甲基肼与亚硝酰钌硝酸根配合物的反应动力学

研究了单甲基肼(MMH)浓度、酸度、温度及预处理时间等对钌预处理效果的影响。采用溶剂萃取法研究了RuNO硝酸根配合物与MMH的反应动力学,75℃下该反应的表观速率方程为:r=Kc6.38(RuNO(Ⅲ)).c2.60(MMH)c-0.88(HNO3)。反应速度随着MMH浓度增加而加快,随着HNO3浓度增加下降。75℃下,料液经MMH预处理2 h,Ru的分配比显著降低,预处理效果明显。     

锝的TBP萃取化学行为研究

报道了在硝酸体系中用３０％ＴＢＰ－正十二烷萃取Ｔｃ（Ⅶ）的实验结果。详细研究了硝酸、硝酸铀酰、硝酸铀（Ⅳ）、硝酸铵、亚硝酸钠、硝酸锆、硝酸钚、硝酸铈，亚硝酰钌、硝酸羟胺、硝酸肼浓度及温度、相比等因素对Ｔｃ（Ⅶ）萃取化学行为的影响。实验结果表明，在不含铀的硝酸体系中，硝酸、硝酸铵、硝酸钚、硝酸锆、硝酸铈、亚硝酸酰钌浓度及萃取温度对Ｔｃ（Ⅶ）的分配比影响很大，而亚硝酸钠、硝酸肼及硝酸羟胺浓度对Ｔｃ（Ⅶ）的分配比影响较小；在含铀的硝酸体系中，硝酸浓度对Ｔｃ（Ⅶ）的分配比有影响，而萃取温度、硝酸钚、锆的影响较小。Ｔｃ（Ⅶ）在含或不含铀的硝酸体系中，与ＴＢＰ分别形成ＵＯ２ＮＯ３·ＴｃＯ４·２ＴＢＰ和ＨＴｃＯ４·３ＴＢＰ萃合物。     

预处理过程对Np(Ⅴ)稳定性的影响

为了提高Purex流程铀纯化循环2D槽中镎的净化效果,研究了Np(Ⅳ)氧化条件,考察了用硝酸肼对钌进行预处理的过程中,预处理试剂浓度、酸度、温度、时间等不同预处理条件对Np(Ⅴ)稳定性的影响.结果表明,在0.2 mol/L酸度、85℃下保温2h,可以将料液中97％的Np(Ⅳ)氧化为Np(Ⅴ)或Np(Ⅵ).预处理时离子强...     

食品中微量~(99)Tc的分析方法研究

正针对食品样品中微量~(99) Tc的分析,建立了一种高效、定量分离~(99) Tc,并能有效除去电感耦合等离子体质谱测量过程中干扰~(99) Tc的钼、钌元素的方法。该方法采用聚乙二醇-4000涂覆的C18-U柱分离锝、钼和钌,用2mol/L碳酸钠溶液体系上柱后,用2mol/L碳酸钠溶液去除Mo和Ru,使用去离子水洗脱吸附在柱上的Tc。C18-U柱上Mo、Ru、Tc的淋洗曲线示于图1。该方法对~(99) Tc的平均回收率接近100%,钼的去污因子为1.3×10~4,钌的去污因子为6.2×10~3,极大地减少了钼、钌对     

羟胺及其衍生物与Pu(Ⅳ)的氧化还原反应定量构效关系

通过Chem3DUltra软件构建羟胺及其衍生物的三维结构,在预优化的基础上,运用gaussian03程序包,采用密度泛函B3LYP方法和6-311+G(3d,3p)基组对6种羟胺及其衍生物进行了几何优化和能量计算,获得了其稳定构型。并利用HyperChem软件包计算优化后的分子的疏水性参数等物理化学参数。运用数学统计软件SPSS对相应的物理化学参数进行相关性分析及逐步回归分析,最终得到具有良好相关性的QSAR方程。方程表明:分子总能量是影响羟胺及其衍生物对Pu(Ⅳ)还原速率的主要因素,且与Pu(Ⅳ)还原速率呈负相关。     

N,N-二甲基羟胺辐解产生的氢气和一氧化碳的研究

With the development of nuclear power industry, more attentions have been paid on reprocessing power reactor spent fuel. Up to now, PUREX process is the only process available commercially. The process achieves uranium and plutonium separation by means of quick and quantitative reduction of Pu (Ⅳ) to Pu (Ⅲ). Therefore the reductant is very important in PUREX process. Preliminary experiment results[1] show that N, N-dimethyl hydroxylamine not only reduces rapidly Np (Ⅵ) and Pu (Ⅳ) to Np (V) and Pu (Ⅲ), but also stabilizes the Np (V)and Pu (Ⅲ) in acid solution. It may become a salt-free reductant with promising future for applications in the area[2]. However, organics decompose under intense radiation environment, and this affects its reduction efficiency,and products from the degradation may affect separation of the radioactive elements.This paper reports the qualitative and quantitative analysis of hydrogen and carbon monoxide produced by 60Co y-ray degradation of N, N-dimethyl hydroxylamine. The analyses of hydrogen and carbon monoxide were performed by gas chromatography, in which a 2m column packed with 5A molecular sieve and thermal conduc tivity detector[3] were used. The analysis of hydrogen employed argon as carrier gas, the column temperature was 80℃ and the detector temperature was 110℃. The analysis of carbon monoxide used hydrogen as carrier gas, the column temperature was 50℃ and the detector temperature was 80 ℃. The results show that when the concentration of N, N-dimethyl hydroxylamine was between 0.1 mol/L and 0.5 mol/L and the dose delivered by the irradiation was 10-1000 kGy, the volume fraction of hydrogen was (8.0-303.9)× 10-3; and the volume fraction of carbon monoxide is (0-1.7)× 10-3. The volume fraction of hydrogen increased with increasing dose, and it has little relationship with concentration change of N, N-dimethyl hydroxylamine when the irradiation dose was bellow 500 kGy, whereas it increased with the increasing concentration of N, N-dimethyl hydroxylamine when the dose was higher than 500 kGy. The volume fraction of carbon monoxide has little relationship with both the irradiation dose and N, N-dimethyl hydroxylamine concentration.     

亚硝酸与肼或羟胺的反应热测量及工艺验证

采用C80微量热仪分别测定了亚硝酸与肼或羟胺的反应热,得到了亚硝酸与肼以不同摩尔比反应时的摩尔反应热：亚硝酸与肼的摩尔比大于2时,消耗单位摩尔肼的反应放热量ΔE₁=284.4 kJ/mol;亚硝酸与肼的摩尔比小于1时,消耗单位摩尔亚硝酸时的反应放热量ΔE₂=166.7 kJ/mol;亚硝酸与肼的摩尔比介于1和2之间时,消耗单位摩尔肼的反应放热量介于ΔE₁和ΔE₂之间。得到了亚硝酸与羟胺以不同浓度比进行反应时的反应热：亚硝酸过量时,消耗单位羟胺的反应放热量为ΔE₄=200.0 kJ/mol;羟胺过量时,消耗单位亚硝酸时的反应放热量为ΔE₅=194.9 kJ/mol。基于获得的亚硝酸与肼或羟胺的反应热数据,对核燃料后处理工艺流程中1BP调料过程中的温度升高情况进行了计算分析,并通过工艺实验进行了验证。     

亚硝酸与肼或羟胺的反应热测量及工艺验证

采用C80微量热仪分别测定了亚硝酸与肼或羟胺的反应热，得到了亚硝酸与肼以不同摩尔比反应时的摩尔反应热：亚硝酸与肼的摩尔比大于2时，消耗单位摩尔肼的反应放热量ΔE₁=284.4 kJ/mol；亚硝酸与肼的摩尔比小于1时，消耗单位摩尔亚硝酸时的反应放热量ΔE₂=166.7 kJ/mol；亚硝酸与肼的摩尔比介于1和2之间时，消耗单位摩尔肼的反应放热量介于ΔE₁和ΔE₂之间。得到了亚硝酸与羟胺以不同浓度比进行反应时的反应热：亚硝酸过量时，消耗单位羟胺的反应放热量为ΔE₄=200.0 kJ/mol；羟胺过量时，消耗单位亚硝酸时的反应放热量为ΔE₅=194.9 kJ/mol。基于获得的亚硝酸与肼或羟胺的反应热数据，对核燃料后处理工艺流程中1BP调料过程中的温度升高情况进行了计算分析，并通过工艺实验进行了验证。     

Effectiveness of DOP mobilizer on the radiolysis of a semi-crystalline ethylene-propylene copolymer

The role of dioctyl phthalate, DOP, added as a radiation stabilizer (mobilizer) to a commercial, medical grade polypropylene has been examined by FTIR and XPS analyses. It was found that the DOP degraded during γ-irradiation to a sterilization dose under vacuum at 298 K and that the degradation products, which included a variety of oxygenated and aromatic compounds, diffused to the polymer surface.     

乙异羟肟酸的合成及其与Pu(Ⅳ),Np(Ⅳ)配合物稳定常数的测定

在乙醇 水体系中 ,用乙酸乙酯和盐酸羟胺为主要原料合成了乙异羟肟酸 (AHA) ,并通过元素分析、红外光谱 (IR)、质谱 (MS)等方法对其结构进行了表征。用TTA萃取法测定了 1mol/LHNO3体系中AHA与Pu(Ⅳ ) ,Np(Ⅳ )配合物的一级累积稳定常数 ,分别为 5 3× 10 12 和 6 1× 10     

有机废液中Pu(Ⅳ)的回收方法研究进展

高放钚废液的回收处理是核工业中的重要环节和技术难点,络合法能够快速地从新鲜有机废液中反萃出Pu(Ⅳ)、短暂放置的钚废液可采用溶剂还原法还原后进行回收,其中简要介绍了无机还原剂Fe(Ⅱ)、U(Ⅳ)和有机无盐还原剂羟胺类衍生物、脲类衍生物、肼类衍生物、醛类、羟肟酸类及醛肟类,并总结了其优缺点。近年来,为解决长期放置的钚废液,电化学法和光化学法得到了初步研究。本文概括了几种回收方法的研究动向,并对其主要问题进行了分析与展望。     

聚丙烯胺肟螯合纤维的辐射合成及对金属离子的吸附性能

利用６０Ｃｏγ预辐照接枝和胺肟化反应合成了聚丙烯胺肟（ＰＰＡＯ）螯合纤维。研究了影响接枝率、胺肟基团含量和吸附容量的因素。结果表明，接枝率随预辐照剂量、反应时间和单体浓度的增加而增加。羟胺溶液的ｐＨ＝７时，胺肟基团含量最高。吸附容量随胺肟基团含量的增加而增加，该纤维对金的饱和吸附容量为０．５１ｍｍｏｌ／ｇ干纤维，对钯和铜也有较高的吸附容量。     

The KSTAR plasma facing components for 2010 operation

The KSTAR plasma facing components (PFCs) consist of inboard limiter, poloidal limiter, divertor, passive stabilizer and neutral beam armor. The main function of the PFCs is to define boundary of operating plasma and to protect the vacuum vessel and in-vessel components such as diagnostic components, in vessel control coil and several kinds of launchers for heating and current drive systems. The divertor is designed to enhance effective particle control to keep high quality plasma with various flexibilities in the shaping control for wide range of operational regime. The passive stabilizer that is made of CuCrZr alloy is designed to passively control the vertical position and MHD instabilities during operation as well as outer boundary of the plasma. Since fabrication has been started for all of the plasma facing components from middle of 2009, the inboard limiter, the divertor, and the passive stabilizer were successfully installed in the vacuum vessel, in turn. Moreover, one set of neutral beam armor and three strings of poloidal limiters were also installed according to the heating system that newly comes in 2010. All the PFCs tiles were baked to 200 °C and the PFC system showed no vacuum leakage and other mechanical troubles. In this paper, key features, fabrication, results of assembly, and baking of the KSTAR PFCs are summarized in detail.     

~(137)Cs稳谱源的研制

通过对~(137)Csγ射线穿过陶瓷体源芯、不锈钢源壳和钨钢壳后衰减规律的研究,参考用户提供的~(137)Cs稳谱源的表面γ剂量率,确定~(137)Cs稳谱源的活度。对陶瓷体源芯吸附性能进行研究,以提高~(137)Cs稳谱源γ射线输出率的一致性,最终确定~(137)Cs稳谱源的制备工艺。经使用证明,该源的γ射线输出率准确、产品一致性好,已应用于岩性密度测井仪测井,可实现~(137)Cs稳谱源的国产化。