氢-水同位素交换及其应用研究进展

简要介绍了氢气与水之间的氢同位素交换(氢—水同位素交换)的原理和相关理论研究,重点阐述了几种主要氢—水同位素交换工艺的研究和应用进展,并对氢—水同位素交换工艺在氢同位素分离中的应用前景进行了评述。     

氢同位素的交换与置换

固体表面吸附的氢同位素具有自发与气相氢同位素交换并达到某种程度平衡的性质，这种交换作用在金属氢化物表面同样存在。由于金属氢化物体系一般具有氢同位素效应，使得交换平衡时气-固相间的同位素丰度发生变化。利用这种性质可以进行金属氢化物柱内氢同位素间的置换，实现工程方面的应用。     

氢-水同位素交换反应热力学理论研究

本文采用量子化学从头计算法对氢同位素分子及相应的氢同位素水分子进行了几何结构优化和振动频率计算,得到了6种氢-水同位素交换体系的热力学函数和气相反应平衡常数。研究结果表明:平衡常数的理论计算值与实验结果吻合,在0.1 MPa和283.2~373.2K的反应条件下,HD-H2O体系平衡常数的计算值与实验值间相对偏差小于6%。     

氢同位素的交换与置换

固体表面吸附的氢同位素具有自发与气相氢同位素交换并达到某种程度平衡的性质,这种交换作用在金属氢化物表面同样存在.由于金属氢化物体系一般具有氢同位素效应,使得交换平衡时气-固相间的同位素丰度发生变化.利用这种性质可以进行金属氢化物柱内氢同位素间的置换,实现工程方面的应用.     

重水中氢氧同位素的质谱分析

用高分辨率质谱计分析了重水中氢与氧的同位素组成；分析了重水的分子组成、质谱中的单电荷离子；利用高分辨率质谱峰相对强度，计算了重水中的氢氧同位素组成。结果表明，高分辨率质谱法分析重水，可同时分析其中的氢同位素和氧同位素，并且用样量小，结果可靠。     

基于两级钯膜反应器的氚水处理技术

为了处理高浓氚水,搭建了一台氢-水同位素交换串联水汽变换的两级钯膜反应器装置,可以实现级联处理工艺.以天然水代替氚水为源项,以D2代替H2开展了除氢实验,最高获得了207.4的除氢因子,验证了两级钯膜反应器用于处理氚水的可行性.通常情况下,水汽变换反应的除氢因子大于氢-水同位素交换反应.其中,氢-水同位素交换中D2/H...     

Ti-Mo互扩散界面吸氢同位素效应的离子束分析研究

为探究Ti-Mo互扩散对金属吸氢的影响,本文采用离子束分析方法对Ti-Mo薄膜的膜-基互扩散界面的吸氢同位素（H和D）效应进行了研究。通过氩离子刻蚀减薄的方法有效降低了表面碳、氧杂质对样品吸氢的影响。吸氢结果表明,对于表面洁净的样品,氢化后固相中氢或氘的浓度均沿着深度随钼原子含量的增加而减小。在单一气体吸氢实验中,氢原子浓度减小的趋势较氘原子缓慢;而在氢氘混合气体吸氢实验中,当容器中的氢氘压强比p(H2)∶p(D2)≥05∶1时,固体中氘氢浓度之比随钼浓度的增加而降低,但当p(H2)∶p(D2)<05∶1时,氘氢浓度之比随钼浓度的增加而升高。因此,由于Ti Mo界面的互扩散,吸氢出现了显著的氢同位素效应,钼的存在不利于体系对氢同位素气体的吸收。     

低温吸附法分离氦气流中氢同位素的实验研究

采用穿透曲线法研究了液氮温度下活性炭、碳分子筛和碳纳米纤维对氢同位素的吸附等温线和同位素效应。结果表明：活性炭和碳分子筛都是良好的吸附剂，碳纳米纤维对氢同位素的吸附量太低而不具备工程应用的可能性。实验还对吸附剂进行了改性处理，考察了改性吸附剂对氢同位素的吸附性能。     

氢同位素分离效应在催化加成反应中的作用——高比度〔4,5-~3H〕去甲斑蝥素的合成

本文描述了借助催化加成反应制备高比度[4,5-~3H]去甲斑蝥素的化学合成法。同时,为了说明氚丰度对于~3H-去甲斑蝥素比度的影响,在不同氚丰度条件下,进行了催化加成反应。阐明了钯催化剂对氢同位素的分离效应。对氕-氚体系而言,分离效应和温度的关系符合lgα_(H-T)=-0.04 138/T的公式。氢同位素的分离效应是导致实际比度较相应丰度条件下应得比度为低的主要因素。所得实验结果和理论分析数据获得了较好的符合。     

氢同位素分馏效应校正技术研究

同位素分馏效应是影响氢同位素准确分析的主要因素.文章对系统校正法、压缩比校正系数法以及实验室标准气体配制技术等进行了论述,给出了两种校正技术的分析结果.结果表明,引入分子泵压缩比校正系数,可很好解决分馏效应对氢同位素准确测定的影响.     

Characteristic of Two-phase Slanting Flow in Rod Bundle

Palladium membrane has been studied for sepration and purification of hydrogen isotopes because of its large permeability. In order to consider permeation of mixture of hydrogen isotopes, solubilities of protium and deuterium in palladium were studied in the temperature range of room temperature to 500°C using breakthrough method. It was observed that solubilities were represented by Sieverts' law and that the separation factor of protium-deuterium binary system was different from the isotope effect ratio. The ideal adsorbed solution theory by Myers and Prausnitz can be applied to estimate the separation factor of protium-deuterium binary system in palladium using the isotope effect ratio observed when protium and deuterium are handled independently. The permeation behavior of multi component hydrogen isotopes through palladium membrane is discussed applying observation on solubilities of this work.     

金属氢化物柱内氕氘间的排代

在ZrCo,LaNi5,LaNi4 .7Al0 .3和Pd等常用金属的氢化物上 ,进行了气 固间氕氘的一维相互排代实验 ,结果表明 :排代效果与温度、气相流速、固相比表面积及分离因子等因素有关 ;室温下Pd氢化物具有最好的排代性能 ,其次是LaNi5,LaNi4 .7Al0 .3,ZrCo。理论研究表明 ,气 固界面的同位素交换规律决定排代效果 ,排代流出曲线可以用塔板理论模型来描述 ,塔板高度是排代效果优劣的标志。决定塔板高度的首要因素是交换平衡程度 ;同等交换平衡程度下 ,氢同位素效应对板高有重要影响。     

用于氢同位素分离的置换色谱分离材料的研究进展

置换色谱法是一种较有优势的氢同位素分离方法,而分离材料的性能是决定置换色谱法分离效果的一个关键因素。目前研究的置换色谱分离材料包括钯材料和很多非钯材料。钯虽然价格昂贵,但由于其出色的分离性能而难以用廉价金属或合金来替代。本文简要介绍了置换色谱法分离氢同位素的原理,重点介绍了几种置换色谱含钯分离材料(纯钯、载钯硅藻土、载钯氧化铝、钯铂合金等)的性能,初步分析了置换色谱分离材料的发展方向。     

The effect of a micro bubble dispersed gas phase on hydrogen isotope transport in liquid metals under nuclear irradiation

The present work intend to be a first step towards the understanding and quantification of the hydrogen isotope complex phenomena in liquid metals for nuclear technology. Liquid metals under nuclear irradiation in, e.g., breeding blankets of a nuclear fusion reactor would generate tritium which is to be extracted and recirculated as fuel. At the same time that tritium is bred, helium is also generated and may precipitate in the form of nano bubbles. Other liquid metal systems of a nuclear reactor involve hydrogen isotope absorption processes, e.g., tritium extraction system. Hence, hydrogen isotope absorption into gas bubbles modelling and control may have a capital importance regarding design, operation and safety.Here general models for hydrogen isotopes transport in liquid metal and absorption into gas phase, that do not depend on the mass transfer limiting regime, are exposed and implemented in OpenFOAM® CFD tool for 0D–3D simulations. Results for a 0D case show the impact of a He dispersed phase of nano bubbles on hydrogen isotopes inventory at different temperatures as well as the inventory evolution during a He nucleation event. In addition, 1D and 2D axisymmetric cases are exposed showing the effect of a He dispersed gas phase on hydrogen isotope permeation through a lithium lead eutectic alloy and the effect of vortical structures on hydrogen isotope transport at a backward facing step.Exposed results give a valuable insight on current nuclear technology regarding the importance of controlling hydrogen isotope transport and its interactions with nucleation event through gas absorption processes.     

高分辨氢同位素质谱仪的研制与应用

基于聚变核材料科研和生产、高温气冷堆产氚、氚放射性环境监测的需要设计了一套用于氢同位素分析的高分辨氢同位素质谱仪（HR-IRMS）,通过简单易操作的压强法配气系统,建立了氢氘氚配气装置。所研制的HR-IRMS仪器分辨率达2210,测量精密度达0.02%,相对原子质量范围为1~150。比对分析表明,其具有良好的运行稳定性和测定结果准确性,可实现氢同位素直接分析。     

Design and development of hydrogen isotope sensor in liquid PbLi

Indian LLCB – TBM uses liquid Lead-Lithium (Pb-Li) as tritium breeder, neutron multiplier and coolant. Tritium bred in liquid PbLi stream has to be recovered by tritium extraction system. Therefore, a reliable sensor with quick response time for measurement of hydrogen isotope is essential.A hydrogen isotope sensor in liquid Pb-Li, based on permeation of hydrogen isotopes through metal (sensor material) is designed. The capsule shaped sensor, made of iron membrane coated with Pd from inside (downstream side), allow hydrogen isotope to permeate through it. The design work mainly includes the selection of proper material, its thickness and surface conditions, which is to be supported by numerical calculations for optimization of maximum permeation flux, fast response and fabricability. The numerical calculation utilizes a physical model having recombination of two hydrogen isotope atoms at the surface and atomic diffusion through the bulk. In this work, design calculations based on numerical simulation and fabrication procedure of the hydrogen isotope sensor are presented.     

气相色谱法在氢同位素分离中的应用

简要介绍了气相色谱法分离氢同位素的原理,重点阐述了利用气相色谱法分离氢同位素的几种主要工艺(洗提色谱法、氢置换色谱法、自置换色谱法和前沿置换色谱法)及其应用进展,并对气相色谱法在氢同位素分离中的应用前景进行了评述。     

Non- classical diffusion processes

This paper surveys quantum effects in diffusion, with special emphasis on isotope effects for hydrogen isotopes in metals. The various possible contributions to the isotope effect are surveyed, and their importance assessed. The bcc metals (V, Nb, Ta) and fee metals (Cu, Ni, Pd) involve different mechanisms, and these are still doubts in detail about some aspects. A full understanding requires knowledge of the hydrogen-metal interactions. Recent theoretical work supports some of the qualitative ideas discussed, and offers promise for future analyses.     

离心萃取级联分离锂同位素的数学模型

萃取法分离锂同位素有望替代汞齐法消除汞害,但需多级萃取才能获得高丰度同位素,采用离心萃取机替代萃取澄清槽形成萃取级联系统可提升分离效率。基于萃取法分离锂同位素、离心萃取分离原理和级联理论,借鉴气体离心级联分离同位素的方法,引入分流比概念,建立了离心萃取级联分离锂同位素单级、多级的数学模型和级联的平衡时间模型,对离心萃取级联分离锂同位素进行计算分析。离心萃取级联是一种类似全回流矩形级联形式,取料量对级联级数有着很大的影响,级联存在最大取料丰度限制,级联平衡时间受到目标丰度和离心萃取机级停留时间(处理能力)影响,采用多步法级联可有效减少平衡时间。该数学模型可指导工艺的设计,为下一步的产业化应用提供理论依据。     

中国HCCB-TBM氚增殖单元三维多物理场耦合氚输运模拟分析

中国氦冷固态实验包层模块(HCCB-TBM)将在国际热核聚变实验堆(ITER)上安装测试,以验证其氚增殖能力与核热移出能力.HCCB-TBM中的氚输运与流体的传热和传质、氢同位素交换、结构材料的SORET效应密切相关.考虑以上物理因素,基于商业软件COMSOL完成了HCCB-TBM氚增殖单元多物理场耦合的氢同位素输运模...