Measurements and analysis of oxygen bubble distributions in LiCl–KCl molten salt

Transparent system experimental studies have been performed to provide measurement and analysis of oxygen bubble distributions at different sparging rates in LiCl–KCl molten salt at 500 °C using a high-speed digital camera and an oxygen sensor. The results reveal that bubble sizes and rise velocities increased with an increase in oxygen sparging rate. The bubbles observed were ellipsoidal in shape, and an equivalent diameter based on the ellipsoid volume was calculated, ranging from 0.00263 m to 0.00407 m. Results also show that the bubble equivalent diameters are normally distributed. A Fanning friction factor correlation was used to predict a bubble's rise velocity. The oxygen mass transfer coefficients were calculated using the oxygenation model; these values were on the order of 10⁻⁴ m/s and followed a decreasing trend corresponding to an increasing bubble size and sparging rate. The diffusivities were calculated based on two different approaches—one based on physics of the bubbles and the other on systematic properties. The diffusivity values calculated from bubble physics are 1.65 × 10⁻⁹ m²/s to 8.40 × 10⁻⁹ m²/s, which are within the range suggested by literature for gases in liquids of a similar viscosity.     

Electrode reaction of the Np3+/Np couple in LiCl–KCl eutectic melts

The electrochemical behaviour of the Np³⁺/Np couple in the LiCl–KCl eutectic salt was investigated by electromotive force measurements, cyclic voltammetry and chronopotentiometry in the temperature region between 723 and 823 K. The standard redox potential of the Np³⁺/Np couple vs Ag/AgCl (1.00 wt %) was measured and given by the equation, E _Np ³⁺ _/Np ^° = –2.0298 + 0.000706 T, where E is in V and T in K. The electrode reaction of the Np³⁺/Np couple was almost reversible under the conditions studied. The diffusion coefficient of Np³⁺, D _Np ³⁺, in the LiCl–KCl eutectic melts between 723 and 823 K was represented by the equation, D _Np ³⁺ = 2.22 × 10^–6 – 6.88 × 10^–9 T + 5.60 × 10^–12 T ² cm² s^–1. The adsorption and desorption peaks of Np at the Mo working electrode caused by underpotential deposition were also observed in the cyclic voltammograms, and the work function of Np was evaluated as 3.04 eV by peak analysis of the cyclic voltammograms.     

Electrochemical behaviour of LaCl3 at tungsten and aluminium cathodes in LiCl–KCl eutectic melt

The electrochemical behaviour of lanthanum was studied at inert tungsten electrode and reactive aluminium electrode in LiCl–KCl eutectic melt in the temperature range 698–798 K using transient electrochemical techniques. Reduction of La(III) to La(0) at the tungsten electrode takes place in a single step. The reduction shows quasi-reversible behaviour for polarization rates, 25 ≤ ν ≤ 150 mV s^?1 and is predominantly controlled by charge transfer of La(III) ions for scan rates higher than 75 mV s^?1. The heterogenous rate constant of the process was estimated from impedance spectroscopy and from the semi-integrals of the cyclic voltammograms. The redox potential of the La(III)/La couple at the Al electrode was observed to be more positive than that at the inert electrode. This potential shift is due to the lowering of the activity of La in the metal phase caused by the formation of the intermetallic compound Al₁₁La₃. Thermodynamic properties such as Gibbs energy of formation of Al₁₁La₃, excess Gibbs energy and the activity coefficient of La in Al were calculated from the open circuit potential measurement.     

A study on the recovery of actinide elements from molten LiCl–KCl eutectic salt by an electrochemical separation

Pyroprocessing is a prominent way for the recovery of the long-lived elements from the spent nuclear fuel. Electrorefining is a key technology for pyroprocessing and generally composed of two recovery steps—deposition of uranium onto a solid cathode and the recovery of TRU (TRansUranic) elements. In this study, it was investigated on electrochemical separation of actinides to develop an actinide recovery system in a molten LiCl–KCl eutectic salt. In the electrorefining experiment, uranium was successfully separated from cerium. The effects of the anode material and the surface area were investigated during the electrolysis experiments for a more efficient electrorefining system. Anode potential decreased with an increasing anode surface area, however, an anode effect was observed in case of a complicated anode structure for high surface area. Glassy carbon was found to be the best anode material among the molybdenum, graphite, glassy carbon, and oxide materials. It was found that the solid cathode with a perforated ceramic container could be one of the candidates for a salt clean-up process to remove residual actinide elements in the salt after the recovery step.     

Molten salt corrosion of high density graphite and partially stabilized zirconia coated high density graphite in molten LiCl–KCl salt

Corrosion studies were performed on uncoated high density graphite and plasma sprayed partially stabilized zirconia (PSZ) coated high density graphite with NiCrAlY bond coat in molten LiCl–KCl eutectic salt at 600 °C for periods of 250 h, 1000 h and 2000 h under inert argon atmosphere. High density graphite showed weight loss while PSZ coated high density graphite showed weight gain. There is no significant attack and degradation of top PSZ coating in molten salt, however microcracks were observed at the bond coat-substrate interface after 2000 h of exposure. PSZ coated high density graphite exhibited excellent corrosion resistance in molten LiCl–KCl salt due to chemical stability and absence of phase transformation as confirmed from scanning electron microscopy, X-ray diffraction and laser Raman studies, however adhesion of the coating has to be improved.     

Electrochemical study of the codeposition of Mg–Li–Al alloys from LiCl–KCl–MgCl<Subscript>2</Subscript>–AlCl<Subscript>3</Subscript> melts

This work presents a novel electrochemical study on the codeposition of Mg, Li and Al on a molybdenum electrode in LiCl–KCl–MgCl₂–AlCl₃ melts at 943 K to form Mg–Li–Al alloys. Cyclic voltammograms (CVs) showed that the underpotential deposition (UPD) of magnesium on pre-deposited aluminum leads to the formation of a liquid Mg–Al solution, and the succeeding underpotential deposition of lithium on pre-deposited Mg–Al leads to the formation of a liquid Mg–Li–Al solution. Chronopotentiometric measurements indicated that the codeposition of Mg, Li and Al occurs at current densities lower than −0.47 A cm⁻² in LiCl–KCl–MgCl₂ (0.525 mol kg⁻¹) melts containing 0.075 mol kg⁻¹ AlCl₃. Chronoamperograms demonstrated that the onset potential for the codeposition of Mg, Li and Al is −2.100 V, and the codeposition of Mg, Li and Al is formed when the applied potentials are more negative than −2.100 V. The diffusion coefficient of aluminum ions in the melts was determined by different electrochemical techniques. X-ray diffraction and inductively coupled plasma analysis indicated that α, α + β and β Mg–Li–Al alloys with different lithium and aluminum contents were obtained via potentiostatic and galvanostatic electrolysis.     

Study on the preparation of Mg–Li–Mn alloys by electrochemical codeposition from LiCl–KCl–MgCl<Subscript>2</Subscript>–MnCl<Subscript>2</Subscript> molten salt

This study presents a novel electrochemical study on the codeposition of Mg, Li, and Mn on a molybdenum electrode in LiCl–KCl–MgCl₂–MnCl₂ melts at 893 K to form different phases Mg–Li–Mn alloys. Transient electrochemical techniques such as cyclic voltammetry, chronopotentiometry, and chronoamperometry have been used in order to investigate the codeposition behavior of Mg, Li, and Mn ions. The results obtained show that the potential of Li metal deposition, after the addition of MgCl₂ and MnCl₂, is more positive than the one of Li metal deposition before the addition. The codeposition of Mg, Li, and Mn occurs at current densities lower than −1.43 A cm⁻² in LiCl–KCl–MgCl₂ (8 wt%) melts containing 2 wt% MnCl₂. The onset potential for the codeposition of Mg, Li, and Mn is −2.100 V. α, α + β, and β phases Mg–Li–Mn alloys with different lithium and manganese contents were obtained via galvanostatic electrolysis from LiCl–KCl melts with different concentrations of MgCl₂ and MnCl₂. The microstructures of typical α and β phases of Mg–Li–Mn alloys were characterized by X-ray diffraction (XRD), optical microscopy (OM), and scanning electron microscopy (SEM). The analysis of energy dispersive spectrometry (EDS) and EPMA area analysis showed that the elements of Mg and Mn distribute homogeneously in the Mg–Li–Mn alloys. The results of inductively coupled plasma analysis determined that the chemical compositions of Mg–Li–Mn alloys correspond with the phase structures of XRD patterns, and lithium and manganese contents of Mg–Li–Mn alloys depend on the concentrations of MgCl₂ and MnCl₂.     

三元体系KCl–KBr–H_2O 323K相平衡理论计算

根据三元体系KCl–KBr–H_2O相平衡实验数据,回归了该体系中K(Cl,Br)固溶体的组成和平衡液相组成对应的二次方程,对固溶体组成的计算值和实验值进行了对比讨论,计算值的偏差范围在0.36%~3.31%;应用文献报道的Pitzer方程参数与温度的关联方程计算了323 K时该三元体系中盐的Pitzer方程单盐参数,并拟合了该三元体系中固溶体K(Cl,Br)和溴盐关联的活度积。在此基础上应用Pitzer方程和粒子群算法(PSO),对323 K时三元体系KCl–KBr–H_2O的溶解度数据进行理论计算,并用计算出的溶解度数据绘制出该三元体系323 K时的相图,计算结果表明,溶解度的理论计算值与实验值吻合好。     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

LiCl对PA1010/LiCl复合材料结构与性能的影响

采用熔融挤出的方法制备了尼龙1010/氯化锂(PA1010/Li Cl)复合材料,研究了Li Cl对PA1010结晶行为和力学性能的影响。结果表明:Li Cl的加入能降低PA1010的结晶温度,使PA1010的结晶度降低,提高复合材料的透明性,当Li Cl质量分数为6%时,PA1010已经完全不能结晶。并且Li Cl的加入能够提高复合材料的拉伸强度和冲击强度,当Li Cl质量分数为4%时,复合材料的冲击强度最大。     

“Ethane oxychlorination” over γ-Al2O3 supported CuCl2–KCl–LaCl3

A study on -Al₂O₃ supported CuCl₂/KCl/LaCl₃ for ethane oxychlorination was carried out by means of XRD, XPS,TGA/DTA, BET TEM and ICP. The experimental results indicate that the catalytic properties of the 5 wt,%Cu–6 wt.%K–5 wt.%La/-A1₂O₃ are optimal. This catalyst was studied in more detail and it was found that deactivation of the catalyst was due to carbon deposition and loss of active species of Cu⁺².     

KCl–K_2SO_4–Na_2SO_4系统低温融体形成的温度范围

KCl–K2SO4–Na2SO4系统低温融体是引起新型干法水泥预分解系统结皮堵塞至关重要的因素。融体的熔点越低,低温融体对粉状物料的粘结能力越强,因而对结皮堵塞的影响也越大。用化学试剂和实验电炉进行实验,绘制了KCl–K2SO4–Na2SO4低温融体形成的温度范围图。结果表明:KCl–K2SO4–Na2SO4三元系统共融温度<800℃,最低共融温度<500℃,相当大范围的共融温度在500～700℃。在Na2SO4含量较高的情况下共融温度低,预示其对结皮影响比K2SO4的更大。     

蒙特斯LiCl除湿机失效与再生

分析了影响蒙特斯蜂窝式氯化锂除湿机除湿能力发挥的各种因素,并提出了“严重”失效的转轮再生方法,使转轮处理后干燥风露点温度更低。     

Effect of oxide ion donors on the corrosion and dechromization of stainless steels in KCl–NaCl–BaCl2 melt

The corrosion behaviour of several austenitic and ferritic stainless steels was studied in the KCl–NaCl–BaCl₂ melt (molar ratio 1:1:1) at 600°C in the absence and presence of 0.1 molal sodium salts with different oxyanions, namely, Na₂CO₃, Na₂O₂, Na₂SO₃, Na₂SO₄, Na₃PO₄ and Na₄P₂O₇. The corrosion rate, determined from analysis of the melt by atomic absorption, was found to agree well with that determined from anodic polarization and decreased with increasing percentage Cr in the alloy. The presence of the oxyanions led to a decrease in the corrosion rate in the order: P₂O ₇ ^4– 4 ^3– 3 ^2– 4 ^2– 2 ^2– 3 ^2– which runs parallel to the order of increasing ability of O^2– ion donation and indicates that the inhibition process involves the formation of a passivating film on the surface. All stainless steels were found to suffer a significant selective leaching of chromium and among all the oxyanions tested, only CO ₃ ^2– anions suppressed the dechromization in the KCl–NaCl–BaCl₂ melt significantly.     

KCl掺杂高纯度方钠石的合成

在硅铝酸盐胶体中掺杂KCl,采用水热法合成了高纯度的方钠石。考察了KCl掺杂量对合成方钠石的影响,研究表明:在不同含水量的硅铝酸盐胶体中掺杂KCl可以合成高纯度的方钠石,合成的方钠石均为球形颗粒,胶体中含水量越高,球形颗粒的粒径越大。为工业合成方钠石提供了一种新方法。     

LiCl溶液除湿系统的试验研究

溶液除湿空气调节装置具有不受气候和地域限制的特点,是最可能被大规模推广的空气调节技术之一。本文进行了逆流填料式单级LiCl溶液除湿过程实验研究,针对除湿过程,研究了进口空气的温度(30~36℃)和相对湿度(50%~70%)对除湿性能的影响。结果表明,除湿性能会随着进口空气温度或相对湿度的升高而增强。此外,针对溶液再生过程,本文考察了再生风进口温度和再生溶液进口温度对再生性能的影响,结果表明,两个温度值的升高均会增大再生能力,且后者的作用更强,但是再生溶液出口温度也会随之上升,从而导致了系统冷源负荷的增大。     

钾盐镀锌液中KCl的测定

1前言 氯化钾镀锌已在电镀行业中得到广泛应用,但对镀液中KCl的测定,文献[1]第82页原文为:"与前面铵盐镀锌中,氯的测定相同."氯的测定是指氯化锌,还是氯化铵的测定呢?若按氯化铵的测定,应按该书第68页方法2,即硝酸银滴定法,计算公式也需做相应修改;而文献[1]并未指明是采用方法1还是采用方法2,也未对计算公式进行修改.     

纤维素LiCl/DMAc体系的溶液特征

本文研究了纤维素LiCl／DMAc体系的溶液特征。实验结果证明该体系具有良好的时间稳定性和热稳定性，能在常温下近30天内没有明显的粘度降低；在100℃高温下，4h不降解。同时测定了溶液的特性粘数和Huggins常数，Huggins常数在0．4～0．6之间，对比纤维素的铜乙二胺（Cuen）溶液，发现特性粘数[η]LICI/DMAc＞[η]Cuen，无扰尺寸ALiCi／DMAc＞ACuen，可见在LiCl／DMAc体系中，溶剂与纤维素分子表现出更强的相互作用力，分子链充分伸展。该体系的特性粘数、粘度常数不仅与温度、溶剂有关，而且是LiCl浓度的函数，具有与聚电解质溶液相类似的性质。这可能是因为纤维素分子链上的H质子和溶液中的Cl-离子相互作用，而使纤维素分子带上部分电荷，相互排斥而引起的。因此利用M－H方程测分子量，粘度常数的确立必须考虑诸多因素的影响，否则会导致分子量的高估。