Kinetic estimation of hydrogen isotope exchange reaction between tritiated-water (HTO) vapor and each amino acid in a heterogeneous system

The hydrogen isotope exchange reaction between HTO vapor and each amino acid has been observed in order to establish a method of estimation of the internal exposure of organically bound tritium in a heterogeneous system at 25～70°C. Rate constants (k) for the amino acids have been obtained by applying the A″-McKay plot method. Using these k values, Arrhenius plots for both the COOH and NH₂ groups are drawn, and linearity was obtained over the range of 25～70°C. Comparing the rate constants, the following four statements can be made regarding the T-for-H exchange reaction. (1) The reactivity of the functional groups in amino acids increases with increasing temperature. (2) Applying Taft's equation, the ratio of polar effect to steric effect is 2:8 in the COOH group and 9:1 in the NH₂ group at 25°C. (3) The A″-McKay plot method is useful for studying the reactivity of materials, not only with one (or the same kind of) functional group(s) but also with two different kinds of functional groups. (4) The method used in this work may be useful to investigate the behavior of organically bound tritium, quantitatively.     

放射性废离子交换树脂高温裂解处理技术研究

通过热重实验以及台架试验,进行了废阴/阳离子交换树脂的高温裂解处理技术研究。结果表明,通过电磁感应加热反应器中的金属球并辅助搅拌,可以实现树脂的高温裂解。相比于氮气和水蒸气,空气是更合适的反应气氛。在空气氛围下,当树脂处理量为1 kg/h时,设定空气流量2 m³/h,反应温度600 ℃～700 ℃,添加剂选择CuSO₄·5H₂O,阴/阳离子交换树脂经本裂解工艺处理,废物残留率分别为8%和12%左右,两种树脂最终的裂解残留率可以达到3%～5%左右,可以实现较为彻底的裂解反应。阴离子和阳离子交换树脂的裂解反应有明显的区别,其中阴离子交换树脂热敏性更高,裂解需要的温度和空气流量更低,但反应更剧烈,烟气量更大。     

冠醚介质中长链卤代烷烃与~(125)I、~(82)Br的交换反应

本文研究了在冠醚介质中~(125)I、~(82)Br与1-Br-十六烷的交换反应,以及不同冠醚、不同阳离子对反应速度和产率的影响。研究了在苯并12-冠-4介质中、~(125)I、~(82)Br与1-Br-十六烷的反应动力学,首次测定了该反应的动力学参数,为短寿命同位素标记化合物的制备提供了快速、有效的新方法。     

金属Ce在高温蒸汽下的氧化动力学初步研究

Ce常用于模拟研究U、Pu等锕系元素的腐蚀行为和转化行为,其在高温水蒸气条件下的氧化动力学目前还未见报道。本研究采用热重分析仪对金属Ce的高温水蒸气氧化动力学开展了研究,得到了动力学曲线,并对反应过程进行了探讨,金属Ce的水蒸气氧化动力学过程呈现明显的三个阶段,反应后主要产物为CeO₂和氢气。     

水热炭球的制备与表征

以葡萄糖为原料,采用水热碳化技术,制备了富含含氧官能团的水热炭球,并采用SEM和FTIR等技术手段对产物的表面形貌和表面官能团结构进行了表征。结果表明：水热炭球的尺寸受葡萄糖溶液浓度、反应温度和有机单体的掺杂等因素影响较大,制得的炭球表面存在丰富的含氧官能团,使其具有良好的亲水性和化学活性。     

Reactivity enhancement of chemical materials used in packed bed reactor of chemical heat pump

In this study, a mixture of expanded graphite (EG) and magnesium hydroxide (Mg(OH)₂) was used to enhance the thermal conductivity and reactivity of a magnesium oxide/water (MgO/H₂O) chemical heat pump, because EG is chemically stable and has high thermal conductivity and high moldability to form the heat exchange structure. Calcium chloride (CaCl₂) was also introduced into the mixture of EG and Mg(OH)₂ to ensure smooth diffusion of vapor in materials and enhance the fittability between EG and Mg(OH)₂. The reaction kinetics of pure Mg(OH)₂, a mixed material containing Mg(OH)₂ and CaCl₂ (termed MC), and a mixed material containing EG, Mg(OH)₂, and CaCl₂ (termed EMC) were examined under the same reaction conditions by performing thermobalance measurements. EMC exhibited a higher dehydration rate than the other materials. It also exhibited hydration reactivity at temperatures of up to 200 °C; at this temperature, pure Mg(OH)₂ exhibited low reactivity. The addition of CaCl₂ also enhanced the hydration reactivity of MgO because of the high water adsorption ability of CaCl₂ in EMC. A reaction rate equation for the hydration of EMC was proposed on the basis of an assumed reaction model. The thermal performance of a MgO/H₂O chemical heat pump manufactured using EMC was evaluated from this equation. EMC was concluded to have good potential for use as a packed bed material in the MgO/water chemical heat pump owing to its low cost, high hydration reactivity, high thermal conductivity, and high moldability to form the heat exchange structure.     

How to effectively compute the reliability of a thermal-hydraulic nuclear passive system

The computation of the reliability of a thermal-hydraulic (T-H) passive system of a nuclear power plant can be obtained by (i) Monte Carlo (MC) sampling the uncertainties of the system model and parameters, (ii) computing, for each sample, the system response by a mechanistic T-H code and (iii) comparing the system response with pre-established safety thresholds, which define the success or failure of the safety function. The computational effort involved can be prohibitive because of the large number of (typically long) T-H code simulations that must be performed (one for each sample) for the statistical estimation of the probability of success or failure. The objective of this work is to provide operative guidelines to effectively handle the computation of the reliability of a nuclear passive system. Two directions of computation efficiency are considered: from one side, efficient Monte Carlo Simulation (MCS) techniques are indicated as a means to performing robust estimations with a limited number of samples: in particular, the Subset Simulation (SS) and Line Sampling (LS) methods are identified as most valuable; from the other side, fast-running, surrogate regression models (also called response surfaces or meta-models) are indicated as a valid replacement of the long-running T-H model codes: in particular, the use of bootstrapped Artificial Neural Networks (ANNs) is shown to have interesting potentials, including for uncertainty propagation. The recommendations drawn are supported by the results obtained in an illustrative application of literature.     

Preliminary Experiments on Hydrogen Isotope Separation by Water-Hydrogen Chemical Exchange under Reduced Pressure

A pressure-reducing method is used effectively in a water distillation process to enhance the equilibrium separation factor. The feasibility of the technique is established through application to a water-hydrogen chemical exchange process using a prototype separation column. Isotope separation experiments examining the water-hydrogen chemical exchange reaction are performed for column pressures of 12–101 kPa, and the separation factors for hydrogen and deuterium are obtained. The HETP (Height Equivalent to a Theoretical Plate) values were distributed in the range of 6 to 15 cm. By reducing the pressure in the column, the process temperature can be lowered without reducing the molar fraction of water vapor in the gas stream. It confirmed that the separation factors under reduced pressure are larger than under atmospheric pressure. This fact demonstrates the effectiveness of reduced pressure in water-hydrogen chemical exchange processes.     

Estimation of the functional failure probability of a thermal-hydraulic passive system by Subset Simulation

In the light of epistemic uncertainties affecting the model of a thermal-hydraulic (T-H) passive system and the numerical values of its parameters, the system may find itself in working conditions which do not allow it to accomplish its function as required. The estimation of the probability of these functional failures can be done by Monte Carlo (MC) sampling of the uncertainties in the model followed by the computation of the system response by a mechanistic T-H code. The procedure requires considerable computational efforts for achieving accurate estimates. Efficient methods for sampling the uncertainties in the model are thus in order.In this paper, the recently developed Subset Simulation (SS) method is considered for improving the efficiency of the random sampling. The method, originally developed to solve structural reliability problems, is founded on the idea that a small failure probability can be expressed as a product of larger conditional probabilities of some intermediate events: with a proper choice of the conditional events, the conditional probabilities can be made sufficiently large to allow accurate estimation with a small number of samples. Markov Chain Monte Carlo (MCMC) simulation, based on the Metropolis algorithm, is used to efficiently generate the conditional samples, which is otherwise a non-trivial task.The method is here developed for efficiently estimating the probability of functional failure of an emergency passive decay heat removal system in a simple steady-state model of a Gas-cooled Fast Reactor (GFR). The efficiency of the method is demonstrated by comparison to the commonly adopted standard Monte Carlo Simulation (MCS).     

氘重氧水液相催化交换法氢正常化工艺研究

液相催化交换法是有效的氢同位素分离方法之一,传统电解法进行氘重氧水氢正常化安全风险大,生产成本高,为此利用液相催化交换法对含氘重氧水进行除氘实验。结果表明,反应温度在30~70 ℃内,随着温度升高,含氘重氧水除氘过程的总体积传质系数（Kya）值先变大后变小,当温度大于60 ℃后,总体积传质系数Kya值逐渐变小,最优反应温度为60 ℃;气液比（摩尔比）在0.5~3.0之间,随着气液比增加,含氘重氧水除氘过程的Kya值愈大,含氘重氧水除氘效果越好,但过大的气液比会引起气液夹带甚至导致液泛,降低反应效率。实验结果可为开展高氘浓度氘重氧水液相催化交换法氢正常化工艺研究提供依据。     

氚水对λ-dsDNA结构影响的拉曼光谱分析和DFT模拟

用拉曼光谱法和密度泛函理论(DFT)研究了氚水与λ双链脱氧核糖核酸(λ-dsDNA)之间的相互作用。拉曼光谱法用于分析不同剂量(50 mGy～8 Gy)HTO(活度浓度1×10⁹ Bq/L和1×10¹¹ Bq/L)和γ射线辐照后λ-dsDNA的结构变化。在低剂量(100～500 mGy)的1×10⁹ Bq/L HTO作用下,HTO主要是通过电离辐射过程中的间接作用,破坏碱基之间的氢键,从而导致碱基的错配和碱基结构的修饰,引起碱基对不配对。而低剂量(50～100 mGy)的1×10¹¹ Bq/L HTO对λ-dsDNA具有类似于γ射线的短期影响,主要是通过射线的直接电离或质子化引起λ-dsDNA基本结构的破坏。此外,高辐射剂量(2～8 Gy)的HTO可能导致呋喃糖环的构象转移或通过氚-氢(T-H)交换反应裂解共价键。通过拉曼光谱标记观察到,HTO的三种作用方式可能最终导致λ-dsDNA骨架构象和λ-dsDNA变性的改变。     

Analysis of fuel temperature effects on reactivity of light water reactor fuel assemblies by using MVP-2 adopting an exact resonance elastic scattering model

Using the continuous-energy Monte Carlo code MVP-2 adopting a resonance elastic scattering model considering the thermal motion of a target nucleus (the exact model) for major heavy nuclides, analysis of fuel temperature effects on reactivity of mockup UO₂ and MOX fuel assemblies for light water reactors was performed, and the results were compared with those of the conventional asymptotic model. A base condition was a hot operating condition with an in-channel void fraction of 40% and fuel temperature of 520 ℃ for the BWR fuel assemblies and a hot zero-power condition with fuel temperature of 284 ℃ for the PWR fuel assemblies. The fuel temperature of a high-temperature condition was 1500 ℃ for both types of assemblies. The calculated results showed that the exact model made the neutron multiplication factors at the high-temperature condition lower by ?220 to ?440 pcm (10^?5 Δk) and the Doppler reactivity between the base- and high-temperature conditions more negative by 7% to 10% compared with those obtained by the asymptotic model. The energy-dependent reaction rates of capture and ν-fission were also analyzed to study the detail mechanism in the effect of the exact model on the assembly reactivity.     

Release behavior of bred tritium from LiAlO2

The release behavior of bred tritium to the blanket purge gas is mainly controlled by such bulk phenomena as tritium forming reaction, diffusion of tritium in grain, interaction of tritium with irradiation defects, and absorption together with such surface phenomena as adsorption, isotope exchange reaction between molecular form hydrogen in purge gas and tritium on grain surface (isotope exchange reaction 1), isotope exchange reaction between water vapor and tritium on grain surface (isotope exchange reaction 2), and water formation reaction at addition of hydrogen. Following the observation of the present authors that the isotope exchange reaction 2 is much faster than the isotope exchange reaction 1, the release curve of bred tritium obtained at purge with humidified gas was used for estimation of the effective diffusivity of bred tritium in LiAlO₂. Then, the effective diffusivity of tritium in grain of LiAlO₂ is obtained as D_T = 2.5 × 10⁻⁷exp(−110 [kJ]/RT) [m²/s]. This equation gives the larger diffusivity than any other diffusivity presented so far because the mass transfer resistance at the grain surface is expected to be eliminated in the estimation procedure of this study.     

Gaseous Exchange Reaction of Deuterium between Hydrogen and Water on Hydrophobic Catalyst Supporting Platinum

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platimun supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms.     

Impact of photoneutrons on reactivity measurements for TMSR-SF1

The solid-fueled thorium molten salt reactor(TMSR-SF1) is a 10 MW_(th) test reactor design to be deployed in 5-10 years by the TMSR group.Its design combines coated particle fuel and molten FLiBe coolant for great intrinsic safety features and economic advantages.Due to a large amount of beryllium in the coolant salt,photoneutrons are produced by(y,n) reaction,hence the increasing fraction of effective delayed neutrons in the core by the photoneutrons originating from the long-lived fission products.Some of the delayed photoneutron groups are of long lifetime,so a direct effect is resulted in the transient process and reactivity measurement.To study the impact of photoneutrons for TMSR-SF1,the effective photoneutron fraction is estimated using k-ratio method and performed by the Monte Carlo code(MCNP5) with ENDF/B-Ⅶ cross sections.Based on the coupled neutronphoton point kinetics equations,influence of the photoneutrons is analyzed.The results show that the impact of photoneutrons is not negligible in reactivity measurement.Without considering photoneutrons in on-line reactivity measurement based on inverse point kinetics can result in overestimation of the positive reactivity and underestimation of the negative reactivity.The photoneutrons also lead to more waiting time for the doubling time measurement.Since the photoneutron precursors take extremely long time to achieve equilibrium,a "steady" power operation may not directly imply a "real" criticality.     

Pt/C对氢同位素交换反应的催化性能研究

采用并流法研究了用不同活性炭担体制备的Pt/C对H2（g）/HDO（v）体系的催化性能,得出Pt/C对氢-水同位素交换反应的活化能为41.3～42.4kJ•mol－1。实验结果表明,采用表面改性活性炭制备的Pt/C对H2（g）/HDO（v）的催化活性比未经改性活性炭制备的Pt/C高出1倍,但两者对水蒸气均为0.77±0.05级反应,其活化能也基本相等,说明活性炭担体表面改性未改变Pt/C对氢-水同位素交换的反应机理。     

二元体系中激发分子反应对正子素(Ps)形成的影响

本文讨论了e~+云团中激发分子反应对Ps形成几率的影响,认为:(1)除了云团中的过剩电子之外,某些激发分子也可以对Ps的形成作出贡献;(2)激发分子与添加剂的反应也能影响Ps形成的几率,并且不同类型的反应(激发分子的猝灭或激发分子与添加剂分子之间发生电子转移)对Ps形成几率的影响也截然不同。根据云团反应的竞争机理,提出了Ps形成几率(三重态正子素O—Ps的几率I_3)与添加剂浓度之间的一般关系式(近似式),并用所得的关系式对一些典型的有机液体与CS_2,SF_6,C_2H_5Br,CCl_4等添加剂组成的混合体系进行了理论拟合,通过对拟合参数的分析,对一些“疑难问题”作出了明确的解释。并把添加剂的电子亲合势和激发分子的电离势等有机地联系了起来。     

碘同位素交换反应在碘吸附器性能评价应用中的可行性研究

依据卤代烃亲核取代反应的特性,设计了碘同位素交换反应制备放射性甲基碘的实验方案。结合核电站现场安全管理要求,对实验试剂进行物性分析和毒理分析。通过实验进行了示踪剂验证、碘同位素交换验证、实验效率分析、实验安全性分析、试剂管理及放射性残液处理等方面的研究,初步验证了用碘同位素交换反应制备放射性甲基碘在碘吸附器性能评价应用中的可行性。     

聚苯乙烯-二乙烯基苯胺肟螯合树脂的辐射接枝合成

以聚苯乙烯-二乙烯基苯（SDB）树脂颗粒为基体，通过预辐照接枝聚合途径在空气气氛中接枝丙烯腈(AN)，然后用盐酸羟胺作功能化处理而引入胺肟基团。采用傅里叶红外光谱仪和扫描电镜等对产物的化学结构及表面微观形貌进行分析。分析结果表明：只有在高吸收剂量（0.6～2.4MGy）条件下才能发生接枝反应，且接枝率随吸收剂量增加而提高。在选定的吸收剂量（2.4MGy）条件下，以丙烯腈单体与水体积比1∶7，于80℃下反应4h所得的接枝产物（SDBAN）再与盐酸羟胺溶液反应，在中性条件下获得了性能良好的偕胺肟基螯合树脂(SDBAO)产物。     

整体式除氚催化剂的制备及催化氧化性能

针对大型核设施产生的大流量废气的处理,发展低气阻的整体式催化剂尤为必要。本工作在整体式堇青石载体上生长分子筛涂层,以离子交换法负载活性组分Pt,获得的整体式催化剂具有高的金属分散度,达到了60%。使用该催化剂,在15℃、体积空速为10 000～40 000 h^-1、1.0%(体积分数)H₂的条件下实现大于99.9%的H₂转化率;在25℃、体积空速为50 000 h^-1、1.0%H₂的条件下实现H₂的完全转化。在更低的H₂浓度下(0.1%H₂和0.5%H₂),该催化剂在湿条件下的H₂转化率低于干条件下的H₂转化率,表明水蒸气会抑制室温催化活性。由于分子筛涂层较Al₂O₃涂层具有更低的吸水性,整体式Pt/sil-cord催化剂在湿条件下具有比Pt/Al₂O₃高得多的...