1,9-双(1''''-苯基-3''''-甲基-5''''-氧代吡唑-4''''-基)壬二酮-[1,9]与TOPO协同萃取钍(Ⅳ)机理的研究

一、前言 1,9-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)壬二酮-[1,9] (简称H_2A)为新近合成的一种双-β二酮螯合剂,它较HPMBP类试剂多一倍螯合功能团,不但能与钍(Ⅳ)形成较稳定的可萃络合物,而且还能与某些中性萃取剂产生协萃作用。本文以氯仿为溶剂研究了它对钍(Ⅳ)的单独萃取及它与三辛基氧膦(TOPO)协同萃取钍的作用,测得了萃合物的组成为ThA_2·TOPO。求得单独萃取和协同萃取反应的平衡常数分别为β_(20)=1.03×10~8和β_(21)=1.18×10~9。     

协同萃取规律的研究 Ⅷ.AAB类三元体系(TTA+PMBP+TOPO)协萃硝酸铀酰研究

本文研究铀(Ⅵ)的三元协萃规律。AAB类是在研究了ABC类(PMBP+TBP+(C_6H_5)_4AsCl)、(TTA+DBSO+(C_6H_5)_4AsCl),ABB类(PMBP+TBP+DPSO)、(HTTA+TBP+DPSO)分别从硫氰酸和硝酸底液萃取U(Ⅵ)基础上,新找到的三元协萃体系。本文报道α-噻吩甲酰三氟丙酮(TTA)与1-苯基3-甲基4-苯甲酰基吡唑啉酮-5(PMBP)、三辛基氧化膦(TOPO)的氯仿溶液,萃取硝酸铀酰的协萃效应。用斜率法确定了二元及三元协萃络合物的组成UO_2(TTA)_2·TOPO、UO_2(PMBP)_2·TOPO、UO_2(TTA)(PMBP)·TOPO,分别求得其协萃反应平衡常数的平均值为1gβA_1B=3.85(TTA+TOPO);1gβA_2B=5.29(PMBP+TOPO);1gβA_1A_2B=4.87(TTA+PMBP+TOPO)。并用锥角模型计算了配位体的立体角系数和,确定了协萃络合物的空间堆积程度。     

双三唑吡啶硝酸溶液反萃TODGA中的Am和Eu

合成了水溶性的2,6-二[1-(羟丙基)-1H-1,2,3-三唑-4-基]吡啶(PTD),研究了以N,N,N′,N′-四辛基-3-氧杂戊二酰胺(TODGA)为萃取剂、正十二烷为稀释剂时,PTD对Am和Eu的反萃行为。研究了两相接触时间、PTD浓度、初始硝酸浓度和温度对Am和Eu分配比的影响。结果表明:Am与PTD形成1∶1型和1∶2型配合物,Eu与PTD形成1∶1型配合物;PTD反萃TODGA-TBP中Am和Eu的反应均为吸热过程。在PTD浓度一定的情况下,反萃硝酸浓度小于0.7 mol/L时,PTD可以实现TODGA中的Am与Eu的反萃分离。     

取代基对二烷基二硫代膦酸分离三价镧系和锕系元素的影响

初步研究了取代基对二烷基二硫代膦酸分离三价镧系和锕系元素的影响。分别以取代基为正辛基、1-甲基庚基、2-乙基己基、2,4,4-三甲基戊基的4种二烷基二硫代膦酸为萃取剂,煤油为稀释剂,测定水相酸度、萃取剂浓度对几种萃取剂萃取示踪量Am（Ⅲ）和Eu（Ⅲ）的影响。结果表明除二正辛基二硫代膦酸萃取示踪量Eu（Ⅲ）外,以lgD对pH作图得到斜率接近3的直线,以lgD对lgc（（HA）2）作图得到斜率接近2的直线。取代基为正辛基、1-甲基庚基、2-乙基己基、2,4,4-三甲基戊基的4种二烷基二硫代膦酸萃取示踪量Am（Ⅲ）的pH1/2分别为2.31、2.56、2.58、3.14;取代基为1-甲基庚基、2-乙基己基、2,4,4-三甲基戊基的3种二烷基二硫代膦酸萃取示踪量Eu（Ⅲ）的pH1/2分别为3.95、4.01、4.42。取代基对二烷基二硫代膦酸萃取Am（Ⅲ）和Eu（Ⅲ）的能力有明显影响,萃取能力按取代基为正辛基、1-甲基庚基、2-乙基己基、2,4,4-三甲基戊基的顺序依次减小,与几种萃取剂的酸性电离常数大小趋势相同,但它们萃取分离示踪量Am（Ⅲ）和Eu（Ⅲ）的分离系数SFAm/Eu则无明显差异。     

1,9-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)壬二酮-[1,9]与中性磷氧萃取剂对铀(Ⅵ)协同萃取的研究

研究了1,9-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)壬二酮-[1,9](H_2A)与三苯基氧膦(TPPO)或三辛基氧膦(TOPO)对铀(Ⅵ)的协同萃取行为。用斜率法测得协萃合物的组成为UO_2A·B(B为TPPO或TOPO),求得了协萃平衡常数。用萃取法制得了固态协萃合物,并对其组成,UV,IR及~1HNMR进行了研究。     

硝酸介质中镅与镧系元素的DPTP分离研究

选定2,6-二-(5,6-二正丙基-1,2,4-三嗪-3-取代)-吡啶(DPTP)萃取体系,以Am和Eu作为三价锕系与镧系元素的代表,实验考察平衡时间、萃取剂浓度、水相酸度等对Am与Eu萃取分配比的影响。在此基础上,提出了DPTP萃取锕系和镧系的概念流程,并用串级实验进行了验证。实验结果表明：经6级萃取、2级洗涤、6级反萃,Am的收率为98.42%,Eu的萃取率小于0.1%;有机相中Am、Eu的反萃率均大于99.9%;分离因子SF_Am/Eu＝45,SF_Eu/Am>10³。     

四乙基双三嗪吡啶与二酰胺荚醚在硝酸介质中对Am(Ⅲ)/Eu(Ⅲ)的协同萃取

以四乙基双三嗪吡啶(C2-BTP)和四种不同链长的N,N,N′,N′-四烷基-3-氧-戊二酰胺(酰胺荚醚:DGA)作为萃取剂、1,2-二氯乙烷作为稀释剂,在硝酸体系中研究了对Am(Ⅲ)和Eu(Ⅲ)的协同萃取行为。结果表明,长链DGA与C2-BTP具有良好的协萃效应,在水相酸度为1.0 mol/L、盐析剂浓度为1.0 mol/L时,C2-BTP与六个碳链DGA(C6-DGA)的混合萃取剂摩尔比为3∶1时,Am(Ⅲ)和Eu(Ⅲ)的分配比(D)比单独使用C2-BTP提高一倍以上,Am(Ⅲ)与Eu(Ⅲ)的分离因子(SF)最高值约为21。利用斜率法分别确定了各个DGA作为单一萃取剂萃取Am(Ⅲ)和Eu(Ⅲ)的平均配位数约为1.5,表明氯代溶剂可能与DGA的配位氧原子发生了相互作用,影响了DGA对Am(Ⅲ)和Eu(Ⅲ)的配位性能。     

PMBP的铀、钍、钆络合物与TOPO协萃体系的热化学

本文用量热滴定法直接测定25℃时PMBP的铀、钍、钆络合物与滴定剂TOPO产生协萃反应过程中吸收或释放的热量。实验发现TOPO与铀、钍只生成一级协萃络合物:UO_2(PMBP)_2·TOPO和Th(PMBP)_4·TOPO;而与钆则生成二级协萃络合物:Gd(PMBP)_3·TOPO和Gd(PMBP)_3·(TOPO)_2。实验中TOPO浓度及滴定体积为已知,选择估计的△H和β值,以M.S.Caceci提供的计算机程序,运用最小二乘分析的反复运算技术,使标准偏差达到指定要求。本法为协萃机理的研究,提供了新的手段。     

酰胺类萃取剂从模拟高放废液中分离锕系和镧系元素的研究

研究了酰胺荚醚N,N,N′,N′-四丁基-3-氧-戊二酰胺（TBOPDA）和N-503（N,N′-二乙基庚酰胺）以及TBOPDA与N-503的组合萃取剂在硝酸介质中对U（Ⅵ）、Pu(Ⅳ)、Am(Ⅲ)、Eu(Ⅲ)和其他一些金属离子的萃取行为,稀释剂为40％正辛醇-煤油。用0.075mol/LTBOPDA+0.5mol/LN-503/40%辛醇-煤油为萃取剂,从模拟高放废液中分离U（Ⅵ）、Pu(Ⅳ)、Am(Ⅲ)和Eu(Ⅲ)的微型混合澄清槽实验结果表明在A槽,大于99.99％的U（Ⅵ）、Pu(Ⅳ)、Eu(Ⅲ)和Am(Ⅲ)被萃入有机相;在R1槽,U（Ⅵ）被定量反萃,83％的Pu(Ⅳ)和36％的Am(Ⅲ)被反萃入水相;在R2槽中残留的Pu(Ⅳ)、Am(Ⅲ)和Eu(Ⅲ)可被定量反萃下来。该流程可有效提取高放废液中的锕系元素,并可对其进行组分离。     

溶剂萃取的协同效应(Ⅲ)——1-苯基,3-甲基,4-苯酰基吡唑酮-[5]与中性磷萃取剂对钍的协同萃取

1.本文研究了1-苯基,3-甲基,4-苯酰基吡唑酮-[5]的苯溶液在0.1N硝酸介貭中对钍的萃取,有很高的萃取率,測定了其組成为ThX_4,平衡常数β_(40)=1.6×10~7。2.1-苯基,3-甲基,4-苯酰基吡唑酮-[5]与甲基膦酸二异戊酯的苯溶液对钍有极明显的协同效应,测求了协萃絡合物的組成为ThX_4和ThX_3(NO_3)·DIAMP的混合物,并求得它們的平衡常数β_(40)和β_(31)。3.当以路易斯碱性更强的三丁基膦氧化物代替甲基膦酸二异戊酯时,协萃系数可增大至10~6,測求了协萃絡合物組成为ThX_4,ThX_3(NO_3)·TBPO和ThX_2(NO_3)_2·2TBPO的混合物,求得了它們的平衡常数β_(31)和β_(22)。4.对协萃效应的机理、中性磷萃取剂路易斯碱性的关系以及协萃絡合物的可能結构进行了討論。     

医源性电离辐射损伤及其生物医学防护

随着核与辐射技术在医学检查、诊断和治疗领域运用的增加,世界范围受照人群不断增多,医源性辐射已成为人类最主要的人工辐射来源之一。医疗机构和个人在选择利用放射手段获取诊断和治疗利益的同时,需要注意和防护伴随的辐射损伤效应。本文介绍了医源性辐射及其危害、机体组织的辐射损伤特性和类型、辐射生物效应分子及效应调节研究的进展,简要概述目前临床已经使用或最具应用潜力的辐射防护策略。     

Distribution and Fixation of Cesium and Strontium in Zeolite A and Chabazite

The selective removal and fixation of Cs and Sr have been studied in zeolite A and chabazite. Cesium ion was preferentially distributed into chabazite with a high distribution coefficient (K _Cs>10³ cm³·g^?1) in the presence of NaCl (10^?1 mol·dm^?3). The K _Sr values for zeolite A attained about 10³ cm³·g^?1 in the pH range of 8～10, and they gradually decreased with an decrease in pH.

The initial rate of Cs adsorption was fairly fast in chabazite, and the adsorption ratio reached almost 100% within a few hours. The adsorption ratio of Sr in binderless A zeolite reached almost 100% after 15 h. The adsorption of Cs and Sr on these zeolites was followed by Langmuir-type isotherm. Cesium forms of these zeolites recrystallized to pollucite (CsAlSi₂O₆) above 900°C for zeolite A and above 1,200°C for chabazite. As for Sr forms, these zeolites changed to SrAl₂Si₂O₆ above 900°C.

These recrystallized phases were suitable hosts for the immobilization of Cs and Sr in the nuclear waste solutions.     

全国核与辐射安全监管信息系统的研究和建议

文章简要介绍了全国核与辐射安全监管信息系统的前期规划建设情况,包括基本建设内容、系统总体架构、以及工作中发现的影响和制约工作开展的主要问题,并提出了建议。     

Development and diversity and defense-in-depth application of ABWR feedwater pump and controller model

This work developed an advanced boiling water reactor (ABWR) feedwater pump and controller model, which was incorporated into Personal Computer Transient Analyzer (PCTran)-ABWR, a nuclear power plant simulation code. The feedwater pump model includes three turbine-driven feedwater pumps and one motor-driven feedwater pump. The feedwater controller includes a one-element/three-element water level controller and a specific feedwater speed controller for each feedwater pump. The performance tests, including step change of dome pressure, feedwater pumps transfer, inadvertent closure of all turbine control valves, and one feedwater pump trip at 100% power, demonstrate the feasibility of dynamic response of stand-alone model and incorporated model. Furthermore, a diversity and defense-in-depth analysis is performed to demonstrate the feasibility for motor-driven feedwater pump as an emergency core cooling system (ECCS) automatic diverse back-up. In Lungmen nuclear power plant (NPP), a diverse manual initiation means for the high pressure core flooder (HPCF) loop C is designed as the back-up of digitalized engineered safety features actuation system (ESFAS). If the motor-driven feedwater pump (MDFWP) can be an automatic digital diverse back-up for ESFAS, Lungmen NPP would be more robust to defend against software common-cause failure (CCF).     

清洁解控和退役若干动向与新发展

对国际辐射防护协会第 1 0届大会 ( IRPA-1 0 )涉及的清洁解控和退役问题作了论述 ,包括排除、豁免、清洁解控和废物最少化 ;退役工程技术的发展 ,包括去污技术、切割解体技术、探测技术 ;介绍了一个研究堆退役例子和加速器退役 ;最后 ,还论及了退役中受关注的一些问题 ,如 :石墨废物、混凝土废物、重水堆退役的氚防护、退役时间和退役废物量等。     

核与辐射风险的认知与沟通

面对公众对核与辐射风险极度敏感的现象,本文阐述了对风险的认知及影响认知程度的因素,介绍了风险沟通的发展阶段和四种类型,并给出了若干有效的风险沟通策略建议。     

Thermophysical and mechanical properties of CrB and FeB

ABSTRACT

Fuel debris in the Fukushima Daiichi nuclear power plant is thought to contain borides that are generated from B₄C control material. In order to successfully devise methods to effectively remove the debris material, characterization of the properties of the fuel debris is essential. This paper presents some of the thermophysical and mechanical properties of two types of borides, FeB and CrB, and compares them with those of Fe₂B and ZrB₂. These are the representative borides that might have been generated in the Fukushima Daiichi (1F) nuclear power plant accident. We observed that the thermal conductivity values of both CrB and FeB are much lower than that of ZrB₂, and are similar to that of Fe₂B. Moreover, the Vickers hardness and fracture toughness of FeB and CrB are almost identical to each other, and similar to those of ZrB₂ and Fe₂B.     

Sorption methods of separating barium and radium,aluminum and gallum,and zirconium and hafnium

Chromatographic methods of separating elements with very similar properties have now been developed. However, a number of these methods are difficult to use industrially as their throughput is low. The efficiency of chromatographic separation methods could be increased considerably by using appropriate complex formers, which decrease the effective concentration of the ions being separated, and,in the first approximation, this is equivalent to a decrease in the amount of elements being separated. The difference in the formation constants of the complex compounds increases the separation coefficient. By investigating chromatographic separation with the use of various complex formers, we found the optimal conditions for separating barium and radium, zirconium and hafnium, and aluminum and gallium. The throughput of these methods, with respect to the macroelement was 15–60 kg/hr per m² of column cross section.     

测温热电偶拔出回收技术及回收处理装置

核电站反应堆测温热电偶回收装置是堆芯热电偶检修、更换、回收的专用设备。本文结合３００ＭＷ反应堆型，介绍了一种结构简单、操作方便、使用安全可靠的热电偶拔出回收技术及回收处理装置。