PdY合金管束的氢渗透性能

PdY合金膜因其具有良好的透氢性能与机械性能,有望应用于聚变堆氢同位素纯化工艺。基于PdY合金膜的服役参数及氚安全要求,有必要研究在低氢压下PdY合金膜的氢同位素渗透特性,为后续设计氢同位素纯化组件提供数据支撑。本工作基于直管外压式PdY扩散器,研究了低氢压（<50 kPa）、工作温度为350~450 ℃条件下,厚度为80 μm的PdY合金薄膜管的氢渗透速率与膜两侧压力、工作温度的关系。结果表明,低氢压下,PdY合金膜的氢渗透规律符合J=Φpⁿ_H-pⁿ_Ld,且压力指数n等于0.9,渗透速率控制机制主要表现为表面过程控速;提高工作温度使得合金膜的渗透通量增大,且温度对扩散过程的影响更大,使渗透过程更加趋于表面控速。此外,计算了该工作温度范围下的渗透系数,并通过阿伦尼乌斯公式推导求得渗透活化能约为24.54 kJ/mol,渗透常数Φ₀为5.86×10^-6 mol/(m·s·kPa^0.9)。低氢压下,该厚度膜的渗透系数可由5.86×10^-6e^-24.54/^(RT) mol/(m·s·kPa^0.9)进行计算。     

基于双塔式氢氦/氚氦混合气的快速分离技术

氢氦/氚氦混合气快速高效地分离与回收是产氚工艺的关键技术之一。利用液氮温度下吸附剂对氢同位素与氦吸附能力的差异,搭建了双塔式固定床低温吸附-解吸分离氢氦/氚氦的实验装置,通过该实验装置开展了不同组成的氢氦、氚氦混合气的分离实验。实验结果表明:采用双塔式固定床低温吸附-解吸法可以实现不同组成的氢氦、氚氦混合气的快速分离,分离后氦中氢的体积分数低于1.2×10-5,氦的纯度可达到99.998 8%,吸附柱的脱氚率大于97%;双塔式固定床低温吸附-解吸法的解吸氢中含有较高浓度的氦,不适于回收氢;在氚氦分离中采用固定床低温吸附柱是可行的,可作为钯膜分离器的辅助单元。     

纯化氢用多孔不锈钢表面的修饰技术

采用浆料涂敷法,将纳米不锈钢粉末沉积在多孔不锈钢载体上,形成孔径依次减小的微孔不锈钢载体,其孔径约为200nm.在压差为0.1MPa时,其干空气渗透率约为200cm3·cm-2·min-1.再经溶胶-凝胶涂敷法,在此载体上沉积TiO2薄膜,其孔径约为100nm,此时的干空气渗透率,在压差为0.1MPa时,约为100cm3·cm-2·min-1.最后经化学镀技术,得到表面较光洁、合金化较完全的钯银合金膜,该膜在压差为0.1MPa、温度为300℃时的渗氢速率在标准状态下达35cm3·cm-2·min-1,氢氦分离因子达500.     

基于氢同位素研究商用钯银合金膜的渗氚性能

钯银合金膜可用于熔盐堆尾气中气态氚（HT和T₂）的分离与纯化。本文研究了厚度为80 μm的钯银合金膜在纯H₂气氛中及Ar气存在下对H₂的分离效果。结果表明,渗氢过程中氢原子在膜内部的体相扩散是控制速率的关键。Ar气存在时,在钯银合金膜工作温度为480 ℃、混合气体进气流速为100 mL/min、氢分压差为20～100 kPa的条件下,钯银合金膜对H₂气的渗透通量随氢分压差的增大而增加,随Ar气浓度的升高而减小。在氢分压差相同的条件下,纯氢的渗透通量明显高于Ar-H₂混合气的渗透通量,说明钯银合金膜受Ar气的影响分离效果变差。渗氢后的钯银合金膜表面变得光滑,有晶界形成。     

氦中痕量H2、D2组分的高精度气相色谱分析

为满足聚变堆氘氚燃料循环工艺气体中痕量氢同位素组分的特殊检测分析要求,需建立快速、高精度的在线分析方法。针对氦中痕量H₂、D₂组分,本工作以高纯氦为载气,在液氮温度下,使用自制改性Al₂O₃毛细管柱进行分离,放电氦离子化检测器进行检测。结果显示,氢氘组分的检测限不高于1×10^-8,保留时间不高于180 s,氢氘组分色谱峰峰面积响应值的相对标准偏差不大于1.0%,分离度大于1.0。本方法具有分析灵敏、快速的优点,为聚变堆包层在氘氚燃料注入系统和氢同位素分离系统中微量氚的安全分析与精确计量提供了一种有效的测量技术。     

纯Ti吸放氢过程研究

对纯Ti在500和580℃下的吸氢速率常数进行了测定。500℃时,纯Ti吸氢速率随循环测试次数增多而变小,且吸氢动力学曲线出现拐点,吸氢时发生α→β和β→δ2次相变。580℃下的吸氢速率较500℃下的明显变快,吸氢动力学曲线为直线,吸氢时未发生β→δ相变。研究了表面及晶粒度对磁控溅射和球磨制备的TiH2放氢过程的影响。结果表明,在相同升温速率下,由磁控溅射和球磨制备的纳米晶氢化物的放氢曲线与块体材料的放氢曲线存在显著差异。此现象与样品中的缺陷结构有关。     

氢氦在钨中的影响的第一性原理研究

采用PBE形式的广义梯度近似(GGA)的第一性原理计算方法研究了氢或氦在钨中产生点缺陷的形成能以及缺陷形成后对钨的弹性的影响;采用同样的方法研究了空位和自间隙原子这两种缺陷。经计算发现:氢氦掺杂在钨的晶体结构中会引起晶体体积的变化,其变化结果跟掺杂的位置有关,在四面体或八面体处的掺杂会使晶体体积增加,替位掺杂会引起晶体体积减小;从形成能来看,氢掺杂在钨中最占优的位置是四面体处,而氦最占优的则是替位掺杂。在几种缺陷中,形成能最小的是氢的四面体掺杂,形成能最大的则是钨的自间隙原子形成;钨中若含有氢或氦的点缺陷,晶体的体弹模量和剪切模量会发生改变,当钨中含有氢替位或自间隙原子时晶体会向塑性改变,含有其他点缺陷时晶体会沿着脆性方向转变。但总体来说带有缺陷的钨仍然具有延展性。值得注意的是,氢或氦在钨中会引起晶体的各向异性,其具体结果与缺陷所处位置相关,只有缺陷属于替位时才不会发生各向异性。本文的研究工作可为第一壁材料的开发提供理论参考。     

α-铁中氦缺陷对氢原子的俘获

体心立方结构的金属铁(α-铁)是聚变反应堆重要的候选结构材料,受氢和氦原子的辐照后可能会发生力学性能的退化。了解氢和氦原子在铁中的聚集行为是反应堆聚变材料研究的重点。本文采用密度泛函理论计算了α-铁中HeHn集团的稳定性,揭示了替代位氦缺陷俘获氢原子的过程和机制,结果表明,1个氦原子最多可俘获4个氢原子,被俘获的氢原子占据氦原子周围的八面体间隙位,且氢原子倾向于彼此聚拢。对氢原子俘获能的计算表明,氢原子足量时,HeH4是α-铁中主要的氢氦集团构型,反之则以HeH2为主。     

非能动氢复合器性能验证试验方法研究

消氢启停阈值和消氢速率是非能动氢复合器的关键性能参数。本文设计了一种直观方便的非能动氢复合器性能验证试验方法:将非能动氢复合器放于密闭容器中，并通入氢气，只要氢复合器启动消氢反应且整条消氢过程曲线在给定值直线A以下，则验证了启动阈值不大于给定值A；只要消氢过程曲线最终的水平段在给定值直线B以下，则验证了停止阈值不大于给定值B；只要氢复合器达到稳定消氢状态，通入容器的氢气质量流量即为消氢速率。本文设计并搭建了试验装置，采用非能动氢复合器样机PARQX-15进行消氢性能验证试验，成功验证了消氢启动阈值<2%（体积浓度，下同），停止阈值<0.5%，消氢速率大于536 g/h，证明了试验方法的实用性和有效性。      

径向流氦氢分离床穿透特性实验与模拟分析

为系统深入研究径向流氦氢分离床的吸附穿透性能,指导结构设计,本研究借助COMSOL Multiphysics软件耦合材料吸氢动力学方程、流体流动动量方程和质量传递方程,建立了径向床穿透数学模型,并结合实验验证了模型的可靠性,利用模型对特性参数进行参数化扫描,分析其对穿透性能的影响。结果表明,穿透实验结果与模拟数据符合较好,模型可靠。通过分析温度、高径比及孔隙率等参数对床体穿透性能的影响,推荐氦氢分离床床体参数如下：床体吸附温度为室温～343 K,在该温度范围内升高温度对传质区长度及出口处浓度-时间曲线影响较小;随着高径比的增加,床体效率明显下降,其中高径比为2.00～8.33时,维持高效率的时间较长;随着孔隙率的增加,床体吸附效率明显下降,考虑床层的吸附效率、压阻效应及粉末的装填难度,粉末孔隙率推荐0.56～0.64。以上结果表明,本研究建立的模型可较好地预测床体的吸附分离性能,可用于床体结构设计以及工艺参数的优化。     

高温气冷堆甲烷蒸汽重整制氢系统重整器性能数值分析

甲烷转化率和产氢量是反映重整器性能的重要指标。本文对匹配高温气冷堆HTR-10的蒸汽重整器性能进行数值分析。设定重整器氦气入口流量不变，研究不同氦气入口温度、压力，不同工艺气入口温度、压力、流量，以及不同水碳比对重整器性能的影响。在所研究的范围内，结果表明：氦气的入口温度对重整器性能有明显的影响；氦气的入口压力、工艺气的入口温度和压力对重整器性能影响较小；提高工艺气流量，甲烷转化率降低，但产氢量增加，而提高水碳比则有相反的变化关系。     

Modeling of the Helium-Heated Steam Reformer for HTR-10

In this study, based on the pseudo-homogeneous one-dimensional model, a steady-state model of the helium-heated steam reformer planned to be connected with the 10 MW high temperature gas cooled reactor (HTR-10) has been developed. Good agreement is shown between the simulating results and experimental data. The influence of main process parameters on the performance with respect to the methane conversion and the hydrogen yield is investigated and discussed. The performance increases remarkably with the increase in the inlet helium temperature when it is lower than 1,000°C. Whereas, the effect becomes weak when the temperature is higher than 1,000°C. The influence of the inlet helium flow rate is not as evident as that of the temperature. The inlet helium pressure and inlet process gas temperature have almost no influence on the performance. The performance increases with the decrease in the inlet process gas pressure. The influence of the inlet process gas flow rate and steam-to-carbon ratio (S/C) is complicated. Optimal values should be chosen for them to obtain a high performance.     

Estimation of the Tritium Behavior in the Pebble Type Gas Cooled Reactor for Hydrogen Production

In Korea, a nuclear hydrogen program has been established to develop and demonstrate mass production system for hydrogen generation. The objective of this study is to establish the evaluation procedure for predicting the tritium behavior in the 300 MWth Pebble type gas cooled reactor which is the one of the candidate reactors for nuclear hydrogen development and demonstration plant. The tritium generated by the fission reaction can be leaked to the helium coolant from the coated ceramic particles and fuel elements. The annual total release rate of the tritium is estimated as 0.47% from the fuel kernel to the helium coolant by the numerical method. Tritium attributed by ⁶Li existing as impurities in the reflector can be released to the helium coolant by the diffusion process and the total annual release rate of the tritium is estimated as 5.3% through the reflector to the helium coolant. Based on the Siverts' law, tritium permeation from the primary coolant to the hydrogen production system is also evaluated and the result is calculated as 76?0.23 Bq/g-H₂ with respect to the PRF (Permeation Reduction Factor= 10?1000) in case of the normal operation of the 300 MWth Pebble type reactor.     

氧化锆检测器在微量氢同位素色谱分析中的应用研究

针对氦气与氢同位素气体热导性差异较小的问题,以氧化锆原电池为气相色谱检测器、改性γ-Al_2O_3为填充柱,在液氮温度(77K)下系统研究了氧化锆检测器测量氢同位素的影响因素,对氦气中微量氢同位素气体进行了分离测试。结果表明,氧化锆检测器的最佳工作温度约为700℃,在载气流速为60mL/min条件下,仪器测量的相对标准偏差小于1%,该方法对H2的检测下限可达15ppm,对D2的检测下限可达40ppm,样品检测的相对误差小于5%。以上结果表明,氧化锆检测器可用于氦气中微量氢同位素的分析测量。     

Helium dilution effect on hydrogen permeation in 316L stainless steel and nickel-base heat-resistant alloys

Effects of inert-gas dilution on hydrogen permeation have been investigated in 316L stainless steel, Inconel 600, Inconel 750, Nimonic 80A and Hastelloy X at 1173 K and 1073 K, by employing a gas-flow system. We used gas mixtures of hydrogen and helium, whose hydrogen concentration ranged from 10^?5 to 10^?1. For the steady-state permeation, the dilution of hydrogen caused no anomalous effects and the permeation rate conformed to Sieverts' law. However, for the transient state, the hydrogen permeation was retarded by the dilution with helium. The retardation effect is discussed in terms of an adsorption model and explained by a decrease in sticking probability at the alloy surface with the dissociative adsorption of hydrogen.     

Effect of Argon Ion Sputtering of Surface on Hydrogen Permeation through Vanadium

In order to measure the hydrogen permeation rate through V with atomically cleaned surface, an Ar ion sputtering apparatus has been installed in the hydrogen permeability measuring system. The permeation rate of the initial specimen was found to be increased by about one order of magnitude after Ar ion sputtering of its upstream side surface. Repeating of such a sputter-cleaning was not so much effective in increasing the steady state permeation rate as the initial sputtering was, but it accelerated the transient response rate by a factor of 2 or 3. The transient response rate was also accelerated by the increase of hydrogen pressure, but this effect tended to be diminished by the sputter-cleaning of specimen surface. The surface impurity layer on the downstream side of specimen was also inferred to act as a diffusion barrier affecting the steady state permeation rate. The present value of activation energy for hydrogen permeation through V at temperatures below 873 K was the smallest one ever obtained, showing that the surface effect was minimized in the present study on account of the surface sputter-cleaning in addition to the ultra high vacuum system.     

低活化铁素体/马氏体钢CLF-1氢氘的渗透行为

低活化铁素体/马氏体钢（RAFM钢）作为聚变堆结构材料中最有前景的候选材料,其氢同位素渗透行为备受关注。采用氢同位素气相驱动渗透的方法,对中国低活化铁素体/马氏体钢CLF-1的氢同位素渗透行为进行了研究,研究了温度、气体压强、样品表面状态等因素对其渗透行为的影响。结果表明：氢、氘在RAFM CLF-1钢中渗透扩散过程为体扩散控制,渗透率与温度的关系式均遵循Arrhenius关系;在实验测试过程中,由于样品表面发生氧化现象和缺陷捕获造成H₂和D₂渗透实验中渗透通量出现下降的现象。