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/H₂O体积流量比越大,该反应除氢因子越大;氢-水同位素交换中原料侧压力越大,该反应除氢因子越大;原料水流量越大,两个反应的除氢因子均会下降。由于一级膜反应器采用氢-水同位素交换可将氚水浓度降低1个量级以上,因而可以尽量避免二级膜反应器中CO与高浓氚接触,抑制含氚有机物的生成。由此可见,两级钯膜反应器有望成为一种高效的氚水处理装置。     

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。     

钯催化H2O2分解的机制探讨

高放废物（HLW）处置库近场地下水的辐解能够产生H₂O₂,其被裂变产物合金颗粒（ε-颗粒）的催化分解属于多相表界面反应。本工作选用钯粉模拟ε-颗粒,采用高压反应釜研究体系总压和H₂分压对反应的影响,并按一级动力学模型拟合实验数据。添加HO·的捕获剂和淬灭剂的实验证明无H₂反应过程中存在HO·的生成步骤。钯的催化活性及形态变化与反应时间的关系表明,产物氧吸附在钯的表面对反应具有毒化作用。通过持续监测滤液中H₂O₂浓度的变化,发现溶液中存在类似于Haber-Weiss的反应持续消耗H₂O₂。推导出钯对H₂O₂分解的机制过程和影响因素,为处置库的安全评估提供基础数据。     

氦中痕量杂质气体气相色谱检测分析方法研究

为实现聚变堆氘氚燃料工艺气中痕量杂质气体组分的快速检测分析,需建立特殊的高精度在线气相色谱检测分析方法。以高纯氦作为载气,在不同的色谱柱温度和载气流速控制下,通过分子筛毛细管柱和PLOT-Q柱进行分离,采用放电氦离子化检测器（DID）进行检测,对氦中含量为1、10以及100 ppm的杂质标准气体进行检测分析。结果表明：在柱温为40 ℃、流速为15～20 mL/min实验条件下,分子筛柱在160 s内能够实现H₂、O₂、N₂、CH₄和CO全部分离,且柱效较高,响应值的重复性较好,H₂和O₂之间的分离度高于1.5,实现了完全分离;在柱温为40 ℃、流速为20 mL/min时,PLOT-Q柱分离CO₂组分效果最佳。     

用于氢同位素纯化的Pd-Zr选择渗氢复合膜

为了获得低成本、高渗氢率、长寿命、高强度的选择渗氢膜,耐熔金属锆(zr)被选作复合膜的基体。在真空度为3.0×10-7Pa下,采用离子轰击刻蚀去除其表面氧化层,实验发现在其表面上仍有少量氧化锆的存在。在真空度为6.6×10-6Pa下,采用离子溅射镀膜法,在锆片直径为50 mm、厚度为0.23 mm的双表面上分别镀上了一层厚约400 nm的钯薄膜。采用X射线衍射(XRD)和X射线光电子能谱(XPS)对锆表面及复合膜表面进行了分析。渗氢实验显示这种复合膜的渗氢系数φ为9.917×10-8mol/m·s·Pa1/2(温度623 K,高压侧0.2 MPa,低压侧0.1 MPa),是相同条件下的商用钯银合金膜的6.8倍。研究结果表明,这种Pd-zr选择渗氢复合膜对核燃料和聚变燃料的纯化及反应堆增殖剂中氚的提取具有很大的应用前景。     

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。     

碘硫循环中Bunsen反应液-液相分离影响因素的实验研究

Bunsen反应液-液相分离是整个碘硫循环的枢纽,H₂SO₄相与HI_x相分离效果直接影响整个循环系统的热效率。为提高两相分离效果和循环效率,对Bunsen反应平衡时液 液相分离特性进行研究。配制H₂SO₄、HI、I₂、H₂O混合溶液,研究实验条件对溶液分离效果的影响。研究结果表明,当n(H₂O)/n(H₂SO₄)小于18时,分层所需碘量随温度变化不大,之后随着溶液温度升高和水量增大,分层所需碘量明显增加;在提升温度和增加碘量的同时减小水量可有效提高溶液分离效果;增大水量可减小副反应进行程度,随着温度升高,抑制作用越明显。通过实验研究最终得到较好的分离条件。     

压水堆大修下行工况冷却剂主要辐解产物计算研究

压水堆大修时活化腐蚀产物源项控制是降低集体剂量最有力的手段，冷却剂辐解的影响必须予以考虑。本文基于水辐解反应动力学原理，构建了冷却剂辐解动力学模型，根据该模型计算得到了主要辐解产物H₂O₂、O₂和H₂在各工况的生成情况，并讨论了微观反应机理。结果表明：(1)在停堆下行过程中，冷却剂温度从310℃逐步下降到60℃，溶解氢浓度逐步降为0，一回路从还原性转为氧化性，H₂O₂和O₂的生成显著上升；(2)温度、B/Li浓度、溶解氢浓度、H₂O₂和O₂初始浓度等多种因素均会影响辐解产物的浓度；(3)H₂O₂和O₂是相互促进生成的关系，H₂可以显著抑制H₂O₂和O₂的生成，但高浓度的H₂O₂     

Ni掺杂对金属V抗毒化性能的影响

采用磁悬浮感应熔炼法制备VNi_0.01合金,完全活化后,在含0.5%CO₂的1.0 MPa毒化气氛中进行吸氘反应。在反应初期VNi_0.01合金与纯V相比,仍保持较快的吸氘速率,随后合金吸氘速率迅速下降直至为零。样品毒化后经加热除气处理,样品室内再次充入1.0 MPa高纯氘气,VNi_0.01合金吸氘速率已恢复至完全活化时的水平,而纯V的吸氘速率则低于初次活化时的吸氘速率。合金经活化后测得其增压性能在300～400 K范围内均优于纯V,因而合金有望用于增压化学床。这些研究结果将为该材料的应用提供直接依据。     

氚老化对钯钇合金膜氢渗透性能的影响

在聚变堆燃料循环系统中,钯合金膜将被用于氢同位素与杂质气体间的渗透分离以及含氚杂质中氚的催化回收。长期连续的氚操作将使合金膜体内因氚衰变而累积3He,产生氚老化效应。本工作研究了贮氚老化对Pd8.5Y0.19Ru（原子百分数）合金膜的氕、氘渗透性能的影响。研究结果表明：对于膜内体氦浓度He/M为0.042的氚老化膜,在573～723K温度范围内,氕、氘渗透率被严重降低,膜的氕氘渗透分离系数则有所提高。     

Effect of water vapor on tritium permeation behavior in the blanket system

It is found that most hydrogen supplied to the purge gas changed to water vapor due to the water formation reaction in the early stage of the blanket operation and that physical or chemical adsorbed water is released in the high concentration into the blanket purge gas when the blanket temperature becomes higher than several hundreds of degrees K if the pre-treatment is not applied to the solid breeder materials. Effect of coexistence of water vapor in the purge gas on permeation behavior of hydrogen through F82H ferritic steel in the breeding part and palladium–silver (Pd–Ag) in the recovery part is discussed because use of them is generally considered for recovery of bred tritium from the solid blanket. Almost no decrease in permeation rate of F82H is observed in this study when water vapor exists in the blanket purge gas. The permeability of hydrogen isotopes through the Pd–Ag pipe gradually decreases when water vapor exists in the blanket purge gas. Properties required in estimation of the hydrogen permeated to the purge gas are experimentally obtained in this study.     

Hydrogen permeation of Hastelloy XR for high-temperature gas-cooled reactors

Hydrogen permeation of Hastelloy XR, which was developed for high-temperature gas-cooled reactors, has been investigated with a simulated gas to the reactor environment, 80% H₂ + 15% CO + 5% CO₂. In this gas environment, Hastelloy XR formed chromium oxide and manganese-spinel oxide on the surface and showed a good quality to prevent hydrogen permeation. The prevention behavior can be interpreted in terms of a hydrogen diffusion model in a uniform oxide layer, and dependences of permeation rate on time and temperature are explained by variation of oxide thickness. The pressure dependence of the permeation rate for the oxidized alloy as well as bare metals obeyed Sieverts' law. The environmental effects on hydrogen permeation are also discussed on the basis of correlation between the characteristics of the surface layer and the permeation behaviors.     

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.     

On the study of catalytic membrane reactor for water detritiation: Membrane characterization

Tritium waste recycling is a real economic and ecological issue. Generally under the non-valuable Q₂O form (Q = H, D or T), waste can be converted into fuel Q₂ for a fusion machine (e.g. JET, ITER) by isotope exchange reaction Q₂O + H₂ = H₂O + Q₂. Such a reaction is carried out over Ni-based catalyst bed packed in a thin wall hydrogen permselective membrane tube. This catalytic membrane reactor can achieve higher conversion ratios than conventional fixed bed reactors by selective removal of reaction product Q₂ by the membrane according to Le Chatelier's Law.This paper presents some preliminary permeation tests performed on a catalytic membrane reactor. Permeabilities of pure hydrogen and deuterium as well as those of binary mixtures of hydrogen, deuterium and nitrogen have been estimated by measuring permeation fluxes at temperatures ranging from 573 to 673 K, and pressure differences up to 1.5 bar. Pure component global fluxes were linked to permeation coefficient by means of Sieverts’ law. The thin membrane (150 μm), made of Pd–Ag alloy (23 wt.%_Ag), showed good permeability and infinite selectivity toward protium and deuterium. Lower permeability values were obtained with mixtures containing non permeable gases highlighting the existence of gas phase resistance. The sensitivity of this concentration polarization phenomenon to the composition and the flow rate of the inlet was evaluated and fitted by a two-dimensional model.     

PdY净化器的氢氦分离性能

对PdY净化器及传统净化器的透氢速率和氢氦分离性能进行了研究,结果表明:PdY净化器透氢速率随压差的增大而增大,压差在0.004~0.04 MPa的范围内,其透氢速率约为传统净化器的3倍;而采用PdY净化器进行氢氦分离时,可显著缩短氢氦分离时间。经过长时间循环分离后,3种组分的氢氦混合气均得到了较好的分离,氦气中氢气体积分数均降至0.03%。     

离心分离大质量数差混合物的实验研究方法

为探究混合物离心分离性能，提出了使用易于分离的气体介质进行实验研究的方法，选取全氟甲基环己烷（C₇F₁₄）/六氟化硫（SF₆）、C₇F₁₄/氙气（Xe）、一氟三氯甲烷（CCl₃F）/乙烯（C₂H₄）气体混合物作为离心分离介质，开展了分离实验。利用分馏装置分别得到了精、贫料中的各组分气体含量，结合质谱分析结果，得到了各组分气体的基本全分离系数与混合物的全净化系数。结果表明：此方法可方便分离轻重气体混合物，针对二元混合物离心分离，能给出全净化系数和各自组分的基本全分离系数，可用于混合物离心分离性能的实验研究。     

Hydrogen cold plasma for synthesizing Pd/C catalysts: the effect of support-metal ion interaction

It has been found that cold plasma is a facile and environmentally benign method for synthesizing supported metal catalysts, and great efforts have been devoted to enlarging its applications. However, little work has been done to disclose the influence mechanism, which is significant for controllable synthesis. In this work, hydrogen cold plasma was adopted to synthesize a palladium catalyst supported on activated carbon(Pd/C-P) using H_2 PdCl_4 as a Pd precursor followed by calcination in hydrogen gas to remove the chlorine ions. The Pd/C-P catalyst was found to be made of larger Pd nanoparticles showing a decreased migration to the support outer surface than that prepared by the conventional thermal hydrogen reduction method(Pd/C-C). Meanwhile, the pore diameter of the activated carbon support is small(~4 nm).Therefore, Pd/C-P exhibits lower CO oxidation activity than Pd/C-C. It was proposed that the strong interaction between the activated carbon and PdCl_4~(2-)and the enhanced metal–support interaction caused by hydrogen cold plasma reduction made it difficult for Pd nanoparticles to migrate to the support outer surface. The larger-sized Pd nanoparticles for Pd/C-P may be due to the Coulomb interaction resulting in the disturbance of the metal–support interaction. This work has important guiding significance for the controllable synthesis of supported metal catalysts by hydrogen cold plasma.     

103Pd-110Agm合金膜制备工艺研究

以103Pd和110Agm 为示踪剂,采用化学镀法制备了103Pd-110Agm合金膜,并优化了制备条件：对制得的103Pd-110Agm合金膜采用γ井型探测器进行定量分析,扫描电镜进行定性分析。结果显示,优化后的镀膜条件为：镀液组成为PdCl2(含放射性103Pd) 、AgNO3、Na2EDTA、NH3 、N2H4;Pd与Ag的摩尔比为9∶1;活化液PdCl2的浓度范围为0.5～2.0 mmol/L;金属离子总浓度为5～7 mmol/L;NH3浓度为2～4 mol/L;pH为10～12;N2H4浓度为10 mmol/L;Na2EDTA浓度为0.15 mol/L;恒温水浴槽保持温度为60 ℃,旋转搅拌器转速为40～60 r/min,反应时间为60 min。在以上镀膜条件下进行化学镀,可得到具有金属光泽的镀层。用载体预处理后,扫描电镜显示,镀层表面有晶粒生长,镀后清晰可见;定性分析结果表明,合金膜中有Pd、Ag元素存在。