温度与气压对LiF蒸发速率的影响

减压蒸馏技术是钍基熔盐反应堆燃料处理中回收和纯化核燃料载体氟盐(7LiF-BeF2)可选的技术。本工作使用自行设计并研制的热失重蒸发炉,通过观察燃料载体盐的主要成分LiF在减压蒸馏过程中的失重行为,研究了蒸发温度和气压对LiF蒸发速率的影响。结果表明:LiF的蒸发速率在随着蒸发温度的升高以及气压下降而增大的变化中存在着明显的拐点,蒸发速率的突变可以用熔盐在低气压条件下的沸腾来解释。并进一步讨论了熔盐的沸腾对减压蒸馏回收和纯化燃料载体氟盐的影响。     

FLi/FLiBe盐中7Li富集度对熔盐快堆钍铀转换性能的影响研究

锂(Li)元素是液态熔盐堆中冷却剂熔盐的重要组成成分,由于6Li相对~7Li具有较大的中子吸收截面,其在冷却剂熔盐中的摩尔含量会影响液态熔盐堆的钍铀转换性能,因此研究~7Li富集度对液态熔盐堆钍铀转换性能的影响十分必要。基于熔盐快堆(Molten Salt Fast Reactor,MSFR)的堆芯结构,分别采用FLi和FLiBe两种不同的冷却剂熔盐,选取范围在99.5%～99.995%的一系列~7Li富集度,借助熔盐堆后处理程序MSR-RS(Molten Salt Reactor Reprocessing Sequence),针对能谱、233U初装量、钍铀转换比、233U净产量和倍增时间、Li的演化以及氚产量等一系列参数进行分析。研究结果表明:在MSFR的堆芯中,较FLiBe而言,采用FLi作载体盐能够获得更好的钍铀转换性能;当~7Li富集度由99.995%变为99.9%时,堆芯钍铀转换比降低约1.6%,氚产量增加约8%。综合考虑燃料制造成本和钍铀转换性能等因素,对于分别采用FLi和FLiBe作载体盐的熔盐快堆MSFR,推荐的~7Li富集度都为99.9%。     

减压蒸馏法对熔盐堆载体盐中氧的去除研究

在熔盐堆核能系统中,为避免载体盐中含氧类杂质离子的腐蚀性及其与UF4燃料反应生成UO2沉淀而造成安全隐患,需严格控制熔盐中的含氧类杂质离子含量.利用自行研制的熔盐减压蒸馏装置,研究了载体盐中主要含氧杂质离子(O2?、NO3?、SO42?、PO43?)在高温低压下的蒸发分离行为,以及温度、压力、熔盐起始氧含量等工艺参数对...     

棒状氢化锆慢化钍基熔盐堆中子学性能优化

氢化锆(ZrH)由于具有耐高温、抗辐照和慢化能力强等优点,是反应堆常用的慢化剂。本工作研究具有钍铀转换能自持运行和较低次锕系核素（MA）产量的ZrH慢化熔盐堆的堆芯物理设计方案。采用MOC程序分析了不同燃料盐对于启堆和增殖性能的影响,为提高钍铀转换性能,对堆芯结构和慢化棒设计进行了优化与分析。结果表明：当熔盐体积比处于0.5~0.9时,ZrH慢化剂可将临界所需要的²³³U浓度降低至2%附近;采用含增殖层设计与FLi燃料盐装载的ZrH慢化熔盐堆,50 a平均钍铀转换比（CR）可达到1.028;移动式ZrH慢化棒堆芯设计可实现38 a的自持运行,且堆芯寿期末的MA产量比慢化棒不移动条件下采用FLi燃料盐和FLiBe燃料盐的MA产量分别减少约43%和8%,低于相同能量输出下石墨慢化熔盐堆的MA产量。     

氧化物沉淀-减压蒸馏耦合分离FLiNaK熔盐中的NdF_3

利用氧化物沉淀-减压蒸馏耦合法研究FLiNaK熔盐体系中氟化物的蒸发行为及稀土Nd的分离。高温下氧化物CaO与稀土氟化物NdF_3反应形成难溶于熔盐的稀土氧化物,通过减压蒸馏蒸发、收集冷凝FLiNaK熔盐,提高稀土与熔盐的分离度,促进熔盐的回收利用。研究表明,含有NdF_3(w=3%)的FLiNaK熔盐中加入CaO,730°C下反应6 h,n(NdF_3):n(CaO)=1:3时NdF_3的转化率达95%。X射线衍射(X-ray Diffraction,XRD)分析表明生成的Nd_2O_3主要沉淀在熔盐的底部。经730°C高温沉淀、930°C熔盐蒸馏,冷凝盐中稀土Nd的去污因子达9.4′105,而未经沉淀处理Nd的去污因子为3.1′104,表明高温沉淀蒸馏耦合法使稀土NdF_3转化为氧化物Nd_2O_3,显著增大稀土与FLiNaK的分离度,提高收集盐的纯度。     

熔盐快堆Th-U燃料循环增殖性能分析

熔盐快堆是当前国际上关注的热点之一,本文基于堆芯结构双流体方案,即裂变熔盐燃料和增殖熔盐介质各自独立冷却循环,利用氟化或氯化熔盐中钍铀重金属盐高温下的高溶解度特性,获得熔盐快堆的高增殖。通过比较钍铀燃料循环熔盐快堆的三种可行性熔盐燃料方案(LiF+ThF_4+UF_4、NaF+ThF_4+UF_4和NaCl+ThCl_3+UCl_3),采用基于反应堆安全分析和设计的综合性模拟程序SCALE(Standardized Computer Analyses for Licensing Evaluation),计算了中子能谱、反应性温度系数,分析了增殖比BR(breeding ratio)受反应堆裂变区、增殖区和ZrC中子反射层的尺寸影响、熔盐中~6Li和~(35)Cl同位素丰度的影响,以及熔盐密度误差对BR计算值的准确性影响、易裂变核素随反应堆运行时间演化等。在钍铀燃料循环熔盐快堆中,通过优化处理得到三种熔盐燃料方案的增殖比BR约为1.2。     

熔盐快堆U-Pu燃料循环增殖性能分析

熔盐快堆增殖是当前国际上关注的热点,本文基于堆芯结构双流体方案,利用氟化或氯化熔盐中铀钚重金属盐高温下的高溶解度特性,获得熔盐快堆的高增殖。对铀钚燃料循环熔盐快堆的三种可行性熔盐燃料方案(LiF+PuF_4+UF_4、NaF+PuF_4+UF_4和NaCl+PuCl_3+UCl_3),采用基于反应堆安全分析和设计的综合性模拟程序SCALE(Standardized Computer Analyses for Licensing Evaluation),计算了中子能谱、反应性温度系数。分析了增殖比BR(Breeding Ratio)受反应堆裂变区、增殖区和中子反射层的尺寸影响,熔盐中~6Li和~(35)Cl同位素丰度对BR的影响,以及BR随运行时间动态变化。计算结果表明:氯盐方案(BR=1.46)与两种氟盐方案(BR≈1.06)相比较,具有更大的增殖能力优势。结合熔盐相图、BR随重金属摩尔浓度变化和BR最大值随熔盐平均工作温度变化曲线,可以在熔盐快堆设计中快速确定熔盐的工作温度、重金属摩尔浓度和反应堆增殖比。     

Ln~(3+)在LnF_3-LiCl-KCl熔盐体系中的电化学行为

钍的分离和再利用是熔盐堆钍铀燃料循环的重要组成部分,钍与裂变产物特别是化学性质相似的镧系元素的分离是熔盐堆氟盐燃料处理的关键之一。利用循环伏安法和方波伏安法研究了773 K下多种镧系元素氟化物(w=3%)在LnF_3-LiCl-KCl熔盐中的电化学行为。研究结果表明:Ce~(3+)和Gd~(3+)在惰性电极上均一步还原为金属,Nd~(3+)则是通过两步反应还原为金属,而Sm~(3+)和Eu~(3+)只能还原为低价态的Sm~(2+)和Eu~(2+);Th和Ln在惰性金属阴极上的析出电位差ΔE均大于0.19 V,在LiCl-KCl熔盐体系中实现Th与Ln的电化学分离在理论上是可行的;与纯氯盐体系相比,少量F-的引入不会改变Ln~(3+)在惰性电极上的电极反应过程,F-的存在使得Ln~(3+)在LiCl-KCl熔盐中的活度降低,从而导致扩散系数减小。此研究结果为了解Th4+)和Ln~(3+)在含F-氯盐体系中的电化学行为和建立可行的分离方法提供了基础实验依据。     

氟化物对LiCl-KCl熔盐蒸馏行为的影响

从含有裂变产物氟化物的氯化物熔盐中分离回收载体盐,对锕系元素和裂变产物氟化物电解分离技术的研发有着重要意义。本文以含有稀土、碱土金属和锆氟化物的LiCl-KCl盐为对象,在1 050 K、130 Pa的条件下,研究了氟化物种类和蒸发比例对LiCl-KCl熔盐减压蒸馏行为的影响。结果表明:随着蒸发比例的增大,5%CeF_3-LiCl-KCl混合盐蒸馏后得到的收集盐中Ce的去污系数逐渐减小。对于含有CeF_3、Nd F_3、LaF_3、SrF_2等氟化物的LiCl-KCl盐,蒸发比例为95%时,对应收集盐中金属元素的去污系数基本维持在103数量级。当混合盐含有EuF_3或ZrF4时,金属元素的去污系数相比于其他元素明显偏低,前者主要是由于相对易挥发EuF_2的存在,而后者是由于ZrF_4较高的蒸气压所致。CeF_3-LiCl-KCl蒸发收集盐的分析结果显示,蒸馏后得到的LiCl-KCl盐组成与原料盐一致,氟含量较低,能满足回收再利用的要求。     

采用SCALE计算氟盐冷却高温堆产氚量的一些问题

氟盐冷却高温堆(Fluoride-salt-cooled High-temperature Reactor,FHR)是以熔融的氟盐(2Li F-Be F2,FLi Be)作为冷却剂、TRISO(Tri-structural Isotropic)颗粒为燃料、石墨为慢化剂的热中子反应堆。FLi Be冷却剂中的6Li、7Li、9Be和19F等核素在中子的辐照下产生氚。氚于高温下在金属材料中具有较强的渗透性,可能对操作人员及公众造成放射性危害。氚与F原子结合生成具有强腐蚀性的TF,可能影响结构材料的力学性能和使用寿命。本文采用SCALE5.1和SCALE6(包括6.1、6.1.2和目前最新发布版本6.1.3,后文若无特别说明,SCALE6均指此三个版本)中的TRITON(Transport Rigor Implemented with Time-dependent Operation for Neutronic depletion)模块计算了典型FHR的产氚量。计算结果表明,在Li元素的产氚计算中,SCALE6的TRITON模块由于对Li元素处理不当,给计算结果带来较大差异,影响了计算的正确性。在计算9Be和19F的产氚量时,由于不同版本的SCALE采用不同的反应通道等原因,计算结果也存在差异。综合分析表明,通过SCALE计算FHR产氚量时应当优先采用SCALE6,为修正Li元素处理不当的问题,需使用TRITON中经COUPLE子模块更新整合后的截面库(TRITON默认为ft33f001)来单独运行ORIGEN-S模块。     

钍基熔盐堆核能系统中熔盐的蒸馏纯化与分离

氟盐具有化学与辐射稳定性高、热容量大、传热性能好、运行温度高和蒸汽压低等优点,被用作熔盐堆的燃料载体和冷却剂。随着熔盐堆技术的发展,开发熔盐的净化、回收工艺非常必要。熔盐减压蒸馏技术基于物质挥发性差异进行组分分离,由于过程操作简单、不引入新的物质等特点,在燃料处理过程中有广泛应用。利用减压蒸馏技术对钍基熔盐堆核能系统的载体盐回收、电解产物纯化、模拟燃料球去除浸渗熔盐等方面进行了研究。研究结果表明,含CsF、SrF_2、LaF_3和ThF_4的FLiNaK盐经减压蒸馏处理,可从FLiNaK中除去SrF_2和LaF_3,去污因子分别为4.4×10~3和1.9×10~3,Th的去污因子为94;通过蒸馏可去除电解产物表面夹带的氟盐,纯化电解产物;燃料球中浸渗熔盐在1 085℃下处理37h可去除石墨球中94%的浸渗熔盐。     

Distillation of cadmium from uranium–plutonium–cadmium alloy

Uranium–plutonium alloy was prepared by distillation of cadmium from U–Pu–Cd ternary alloy. The initial ternary alloy contained 2.9 wt% U and 8.7 wt% Pu other than Cd, which were recovered by molten salt electrolysis with liquid Cd cathode. The distillation experiments were conducted in 10 g scale of the initial alloy using a small-scale distillation furnace equipped with an evaporator and a condenser in a vacuum vessel. After distillation at 1073 K, the weight of the residue was in good agreement with that of the loaded actinides, where the content of Cd decreased to less than 0.05 wt%. The uranium–plutonium alloy product was recovered without adhering to the yttria crucible. The cross section of the product was observed using electron probe micro-analyzer and it was found to consist of a dense material. Almost all of the evaporated Cd was recovered in the condenser and so enclosed well in the apparatus.     

Chemistry and technology of Molten Salt Reactors - history and perspectives

Molten Salt Reactors represent one of promising future nuclear reactor concept included also in the Generation IV reactors family. This reactor type is distinguished by an extraordinarily close connection between the reactor physics and chemical technology, which is given by the specific features of the chemical form of fuel, representing by molten fluoride salt and circulating through the reactor core and also by the requirements of continuous ‘on-line’ reprocessing of the spent fuel. The history of Molten Salt Reactors reaches the period of fifties and sixties, when the first experimental Molten Salt Reactors were constructed and tested in ORNL (US). Several molten salt techniques dedicated to fresh molten salt fuel processing and spent fuel reprocessing were studied and developed in those days. Today, after nearly thirty years of discontinuance, a renewed interest in the Molten Salt Reactor technology is observed. Current experimental R&D activities in the area of Molten Salt Reactor technology are realized by a relatively small number of research institutions mainly in the EU, Russia and USA. The main effort is directed primarily to the development of separation processes suitable for the molten salt fuel processing and reprocessing technology. The techniques under development are molten salt/liquid metal extraction processes, electrochemical separation processes from the molten salt media, fused salt volatilization techniques and gas extraction from the molten salt medium.     

金属钠蒸发行为研究#br#

钠的蒸发问题在钠冷快堆技术发展中不容忽视,钠蒸气将会引起众多钠冷快堆的运行问题。通过设计钠蒸发釜,搭建钠蒸发装置,对系列温度和压力下的钠蒸发速率进行了研究。经过大量实验,获得了温度200～550 ℃,氩气压力为5 Pa~51 MPa（a）下钠的蒸发速率。同时研究了蒸发面积、冷却面与钠液面距离对钠蒸发速率的影响。经过对实验数据拟合的结果表明,在同一压力下,钠的蒸发速率随温度的升高而呈指数升高,其变化规律符合Langmuir公式;在相同温度下,钠的蒸发速率随着氩气压力的升高呈对数下降,且与氩气压力自然对数的四项式相关;对于温度和压力的综合影响,得到了两个拟合关系式,该蒸发速率关系式能应用于5 Pa～51 MPa(a)、200～550 ℃范围内钠蒸发速率的预估。     

Process optimization of a closed-chamber distillation system for the recovery of FLiNaK molten salt

Low-pressure distillation has been proposed as a suitable technique for the recovery of carrier salt from molten salt reactor spent fuel. A closed-chamber disti...     

On the separation of lithium isotopes by the method of molecular distillation of liquid lithium

This study determines the value of the separation factor of lithium isotopes in the evaporation of liquid metallic lithium in a single-stage still. At a temperature of 500 °C the value of the separation factor is 1.08 ± 0.02. We carried out studies of the separation of lithium isotopes by the method of molecular distillation in an 8 -stage cascade-type metal still. It was shown that when the cells of the still are filled with metallic packing and the condensation temperature of the lithium is raised to 350 °C, the efficiency of one stage of the still is 0.4–0.5.     

Feasibility of the electrochemical way in molten fluorides for separating thorium and lanthanides and extracting lanthanides from the solvent

An alternative way of reprocessing nuclear fuel by hydrometallurgy could be using treatment with molten salts, particularly fluoride melts. Moreover, one of the six concepts chosen for GEN IV nuclear reactors (Technology Roadmap - http://gif.inel.gov/roadmap/) is the molten salt reactor (MSR). The originality of the concept is the use of molten salts as liquid fuel and coolant. During the running of the reactor, fission products, particularly lanthanides, accumulate in the melt and have to be eliminated to optimise reactor operation. This study concerns the feasibility of the separation actinides-lanthanides-solvent by selectively electrodepositing the elements to be separated on an inert (Mo, Ta) or a reactive (Ni) cathodic substrate in molten fluoride media. The main results of this work lead to the conclusions that:

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The solvents to be used for efficient separation must be fluoride media containing lithium as cation.

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Inert substrates are suitable for actinide/lanthanide separation; nickel substrate is more suitable for the extraction of lanthanides from the solvent, owing to the depolarisation occurring in the cathodic process through alloy formation.

     

液态熔盐热堆燃料管理方法研究与分析

为研究液态熔盐热堆的燃料管理性能,需解决复杂堆芯结构的均匀化、燃料的混合及在线后处理3个问题。本文基于确定论程序DRAGON5与DONJON5,开发了液态熔盐热堆的燃料管理程序LMSR,并进行了验证。使用LMSR对液态熔盐热堆进行计算与分析,结果显示使用²³⁵U与²³⁸U启堆,加入燃料为²³²Th与²³³U条件下,后处理提取重金属的效率至少需要90%。此外,为维持堆芯有效增殖因数在1.0～1.005之间,加入的燃料中²³³U平均等效质量富集度在40%附近。