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Corrosion behavior of metallic alloys in molten chloride salts for thermal energy storage in concentrated

Wenjin Ding, Alexander Bonk, Thomas Bauer

《化学科学与工程前沿（英文）》 2018年 第12卷 第3期   页码 564-576 doi: 10.1007/s11705-018-1720-0

摘要：

Recently, more and more attention is paid on applications of molten chlorides in concentrated solar power (CSP) plants as high-temperature thermal energy storage (TES) and heat transfer fluid (HTF) materials due to their high thermal stability limits and low prices, compared to the commercial TES/HTF materials in CSP-nitrate salt mixtures. A higher TES/HTF operating temperature leads to higher efficiency of thermal to electrical energy conversion of the power block in CSP, however causes additional challenges, particularly increased corrosiveness of metallic alloys used as containers and structural materials. Thus, it is essential to study corrosion behaviors and mechanisms of metallic alloys in molten chlorides at operating temperatures (500–800 °C) for realizing the commercial application of molten chlorides in CSP. The results of studies on hot corrosion of metallic alloys in molten chlorides are reviewed to understand their corrosion behaviors and mechanisms under various conditions (e.g., temperature, atmosphere). Emphasis has also been given on salt purification to reduce corrosive impurities in molten chlorides and development of electrochemical techniques to in-situ monitor corrosive impurities in molten chlorides, in order to efficiently control corrosion rates of metallic alloys in molten chlorides to meet the requirements of industrial applications.

关键词： corrosion mechanisms     impurities     metallic corrosion     salt purification     electrochemical techniques    

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Effects of additive NaI on electrodeposition of Al coatings in AlCl

Tianyu Yao, Haiyan Yang, Kui Wang, Haiyan Jiang, Xiao-Bo Chen, Hezhou Liu, Qudong Wang, Wenjiang Ding

《化学科学与工程前沿（英文）》 2021年 第15卷 第1期   页码 138-147 doi: 10.1007/s11705-020-1935-8

摘要： Effects of NaI as an additive on electrodeposition of Al coatings in AlCl -NaCl-KCl (80-10-10 wt-%) molten salts electrolyte at 150°C were investigated by means of cyclic voltammetry, chronopotentiometry, scanning electron microscopy and X-ray diffraction (XRD). Results reveal that addition of NaI in the electrolyte intensifies cathodic polarization, inhibits growth of Al deposits and increases number density of charged particles. The electrodeposition of Al coatings in the AlCl -NaCl-KCl molten salts electrolyte proceeds via three-dimensional instantaneous nucleation which however exhibits irrelevance with NaI. Galvanostatic deposition results indicate that NaI could facilitate the formation of uniform Al deposits. A compact coating consisting of Al deposits with an average particle size of 3 μm was obtained at a current density of 50 mA∙cm in AlCl -NaCl-KCl molten salts electrolyte with 10 wt-% NaI. XRD analysis confirmed that NaI could contribute to the formation of Al coating with a preferred crystallographic orientation along (220) plane.

关键词： NaI     additive     electrodeposition     molten salts     Al coating    

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Thermal defluorination behaviors of PFOS, PFOA and PFBS during regeneration of activated carbon by molten

《环境科学与工程前沿（英文）》 2022年 第16卷 第8期 doi: 10.1007/s11783-022-1524-9

摘要：

• New method of mineralizing PFCs was proposed.

关键词： PFCs     Molten sodium hydroxide     Thermal degradation     Activated carbon regeneration    

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Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration

Shenghui Zhou, Kuiyi You, Zhengming Yi, Pingle Liu, Hean Luo

《化学科学与工程前沿（英文）》 2017年 第11卷 第2期   页码 205-210 doi: 10.1007/s11705-017-1625-3

摘要： Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO to nitrobenzene under solvent-free conditions. Several salts including FeCl , ZrCl , AlCl , CuCl , NiCl , ZnCl , MnCl , Fe(NO ) ·9H O, Bi(NO ) ·5H O, Zr(NO ) ·5H O, Cu(NO ) ·6H O, Ni(NO ) ·6H O, Zn(NO ) ·6H O, Fe (SO ) , and CuSO were examined and anhydrous FeCl exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.

关键词： metal salts     electronegativity     nitrobenzene     NO2     catalytic nitration    

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Dynamic characteristics of molten droplets and hot particles falling in liquid pool

Liangxing LI, Weimin MA, Huixiong LI, Tingkuan CHEN,

《能源前沿（英文）》 2010年 第4卷 第2期   页码 246-251 doi: 10.1007/s11708-009-0077-y

摘要： The dynamic characteristics of molten droplets and hot particles at the very beginning of their fall into coolant pools are presented. The falling course of a single droplet or a single hot particle was recorded by a high-speed camera and a curve of velocity . time was obtained. Emphasis was placed on the effects of the droplet’s size and temperature, the coolant’s temperature and properties, and the droplet’s physical properties on the moving behavior. The results for the all cases showed that the velocity of a falling droplet/particle decreased rapidly but rebounded shortly, at the beginning of droplet/particle falling in the coolant. Following such a V-shaped evolution in velocity, the droplet/particle slows down gradually to a comparatively steady velocity. An increase in either coolant temperature or droplet temperature results in a larger velocity variation in the “J-region”, but a smaller deceleration when it moves out of the “J-region”. The elevated volatility of a coolant leads to a steeper deceleration in the “J-region” and beyond. The bigger size of a particle leads to a greater velocity variation in the “J-region” and terminal velocity. A high melting point and thermal conductivity as well as lower heat capacity contribute to dramatic variation in the “J-region” and low terminal velocity.

关键词： dynamic characteristics     molten droplets     high-temperature particles     fuel and coolant interactions    

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Analysis of molten metal spreading and solidification behaviors utilizing moving particle full-implicit

《能源前沿（英文）》 2021年 第15卷 第4期   页码 959-973 doi: 10.1007/s11708-021-0753-0

摘要： To retrieve the fuel debris in Fukushima Daiichi Nuclear Power Plants (1F), it is essential to infer the fuel debris distribution. In particular, the molten metal spreading behavior is one of the vital phenomena in nuclear severe accidents because it determines the initial condition for further accident scenarios such as molten core concrete interaction (MCCI). In this study, the fundamental molten metal spreading experiments were performed with different outlet diameters and sample amounts to investigate the effect of the outlet for spreading-solidification behavior. In the numerical analysis, the moving particle full-implicit method (MPFI), which is one of the particle methods, was applied to simulate the spreading experiments. In the MPFI framework, the melting-solidification model including heat transfer, radiation heat loss, phase change, and solid fraction-dependent viscosity was developed and implemented. In addition, the difference in the spreading and solidification behavior due to the outlet diameters was reproduced in the calculation. The simulation results reveal the detailed solidification procedure during the molten metal spreading. It is found that the viscosity change and the solid fraction change during the spreading are key factors for the free surface condition and solidified materials. Overall, it is suggested that the MPFI method has the potential to simulate the actual nuclear melt-down phenomena in the future.

关键词： molten metal spreading     solidification     particle method     severe accident     fuel debris     decommissioning    

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Phenomena identification and ranking table exercise for thorium based molten salt reactor-solid fuel

Xiaojing LIU, Qi WANG, Zhaozhong HE, Kun CHEN, Xu CHENG

《能源前沿（英文）》 2019年 第13卷 第4期   页码 707-714 doi: 10.1007/s11708-019-0616-0

摘要： Thorium based molten salt reactor-solid fuel (TMSR-SF) design is an innovative reactor concept that uses high-temperature tristructural-isotropic (TRISO) fuel with a low-pressure liquid salt coolant. In anticipation of getting licensed applications for TMSR-SF in the future, it is necessary to fully understand the significant features and phenomena of TMSR-SF design, as well as its transient behavior during accidents. In this paper, the safety-relevant phenomena, importance, and knowledge base were assessed for the selected events and the transient of TMSR-SF during station blackout scenario is simulated based on RELAP/SCDAPSIM Mod 4.0. The phenomena having significant impact but with limited knowledge of their history are core coolant bypass flows, outlet plenum flow distribution, and intermediate heat exchanger (IHX) over/under cooling transients. Some thermal hydraulic parameters during the station blackout scenario are also discussed.

关键词： phenomena identification and ranking table (PIRT)     thorium based molten salt reactor-solid fuel (TMSR-SF)     safety analysis     RELAP/SCDAPSIM    

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Multi-objective optimization of molten carbonate fuel cell system for reducing CO

Ramin ROSHANDEL,Majid ASTANEH,Farzin GOLZAR

《能源前沿（英文）》 2015年 第9卷 第1期   页码 106-114 doi: 10.1007/s11708-014-0341-7

摘要： The aim of this paper is to investigate the implementation of a molten carbonate fuel cell (MCFC) as a CO separator. By applying multi-objective optimization (MOO) using the genetic algorithm, the optimal values of operating load and the corresponding values of objective functions are obtained. Objective functions are minimization of the cost of electricity (COE) and minimization of CO emission rate. CO tax that is accounted as the pollution-related cost, transforming the environmental objective to the cost function. The results show that the MCFC stack which is fed by the syngas and gas turbine exhaust, not only reduces CO emission rate, but also produces electricity and reduces environmental cost of the system.

关键词： molten carbonate fuel cell (MCFC)     multi-objective optimization (MOO)     Pareto curve     genetic algorithm     CO2 separation    

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A new regeneration approach to cation resins with aluminum salts: application of desalination by its

Zhigang LIU, Shaomin ZHU, Yansheng LI

《环境科学与工程前沿（英文）》 2012年 第6卷 第1期   页码 45-50 doi: 10.1007/s11783-010-0262-6

摘要： A novel method for the regeneration of cation exchange resins by aluminum (Al) salts was investigated in order to improve the regeneration efficiency of resins and reduce the dosage of regenerant. The influences of Al concentration and the pH of regeneration solution on resin transformation had been studied. The desalination experiments were carried out to evaluate the characteristics of the Al form resins. Experimental results showed that the regeneration rate of resins was strictly dependent on Al concentration and the pH of the solution. Compared to the conventional regeneration method, the Al form mixed bed exhibited the same desalination capability as the H form mixed bed (MB), and the total organic carbon (TOC) removal was up to 90%, clearly higher than that of the H form. Al salt solution could be utilized repeatedly to regenerate Al form resins.

关键词： aluminum (Al) form resins     desalination     mixed bed (MB)     regeneration    

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钍基熔盐堆材料发展战略

周兴泰,李志军,陆燕玲,黄鹤飞,贺周同,戴志敏,徐洪杰

《中国工程科学》 2019年 第21卷 第1期   页码 29-38 doi: 10.15302/J-SSCAE-2019.01.005

摘要：

作为第四代核裂变反应堆之一，熔盐堆由于其高的能量转换效率、固有安全性、适合钍燃料的利用等优越性，在世界范围内受到越来越多的关注。熔盐堆主要构件需要在高温、氟化物熔盐腐蚀及中子辐照等极端工作环境下长期稳定、安全有效地工作，因而对其所用材料提出了极大的挑战。本文从熔盐堆工况特点及其对材料的基本需求出发，描述了熔盐堆关键材料（包括合金结构材料及核石墨）的发展历程、现状及存在的问题，特别指出了针对目前实验堆建设阶段需要解决的关键科学技术问题，围绕熔盐堆研发计划，规划了熔盐堆材料未来的发展方向及路线图。

关键词： 熔盐堆     高温材料     材料–熔盐相容性     辐照效应    

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Estimation of thermodynamic properties of the ternary molten salt system, LiF-NaF-BeF2, by the modified

ZHANG Dalin, QIU Suizheng, SU Guanghui, JIA Dounan

《能源前沿（英文）》 2007年 第1卷 第2期   页码 174-180 doi: 10.1007/s11708-007-0022-x

摘要： The molten salt reactor (MSR), which is one of the generation IV reactors, can meet the demand of transmutation and breeding. The thermodynamic properties of the molten salt system like LiF-NaF-BeF2 influence the design and construction of the fuel salt and coolant in the MSR for the new generation. In this paper, the equation of state of the ternary system 15%LiF-58%NaF-27%BeF, over the temperature range from 873.15 to 1 073.15 K at one atmosphere pressure, is described using a modified Peng-Robinson (PR) equation. The densities of the ternary system and its components are estimated by this equation directly, and compared with the experimental data. Based on the equation of state, the other thermodynamic properties such as the enthalpy, entropy and heat capacity at constant pressure are estimated by the residual function method and the fugacity coefficient method respectively. The densities calculated by PR equation are highly in agreement with the experimental data, and the enthalpy, entropy and heat capacity evaluated by the two different methods are consistent with each other. It can be concluded that the modified PR equation can be applied to evaluate the density of the molten salt system, and it is recommended that it be used as the basis to estimate the enthalpy, entropy and heat capacity of the molten salt system.

关键词： modified Peng-Robinson     coolant     consistent     MSR     entropy    

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循环热载体无烟燃烧技术的试验研究

何方,王华,戴永年

《中国工程科学》 2004年 第6卷 第7期   页码 65-69

摘要：

提出了一个基于熔融盐循环热载体的无烟燃烧技术，即把一个燃烧过程分为氧化剂生成和燃料燃烧两个步骤进行，燃烧过程能使助燃空气中的N<sub>2</sub>和燃烧产生的CO<sub>2</sub>在一套反应装置中进行分离，得到较高纯度的N<sub>2</sub>和CO<sub>2</sub>，N<sub>2</sub>可回收利用，CO<sub>2</sub>则可捕集起来安全封存。整个燃烧过程避免了向大气排放有害气体；以CuO为催化剂，对CH<sub>4</sub>在Li<sub>2</sub>CO<sub>3</sub>-K<sub>2</sub>CO<sub>3</sub>-Na<sub>2</sub>SO<sub>4</sub>熔盐体系中的熔融燃烧过程进行的试验研究结果表明，CH<sub>4</sub>能在该熔融盐体系中能完成无烟燃烧过程并放出热，失去晶格氧的CuO能与空气反应重新恢复其晶格氧，气相色谱分析结果显示，理想的反应条件下, 得到的N<sub>2</sub>的纯度为99.<sub>3</sub>%以上，CO<sub>2</sub>的纯度为95.1%以上。

关键词： 无烟燃烧技术     熔融盐     温室气体    

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Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NO

Biwu CHU, Jiming HAO, Junhua LI, Hideto TAKEKAWA, Kun WANG, Jingkun JIANG

《环境科学与工程前沿（英文）》 2013年 第7卷 第1期   页码 1-9 doi: 10.1007/s11783-012-0476-x

摘要： Aerosol phase reactions play a very important role on secondary organic aerosol (SOA) formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate (MnSO ) and zinc sulfate (ZnSO ), on the photochemical reactions of a toluene/NO photooxidation system in a 2 m smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NO conversion and the formation of ozone and SOA. MnSO and ZnSO seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO and ZnSO seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.

关键词： manganese sulfate     zinc sulfate     seed aerosols     toluene photooxidation     secondary organic aerosol    

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Corrosion behavior of Fe–Cr–Ni based alloys exposed to molten MgCl2–KCl–NaCl salt with over-added

《化学科学与工程前沿（英文）》 2023年 第17卷 第10期   页码 1608-1619 doi: 10.1007/s11705-023-2349-1

摘要： MgCl2–NaCl–KCl salts mixture shows great potential as a high-temperature (> 700 °C) thermal energy storage material in next-generation concentrated solar power plants. Adding Mg into molten MgCl2–NaCl–KCl salt as a corrosion inhibitor is one of the most effective and cost-effective methods to mitigate the molten salt corrosion of commercial Fe–Cr–Ni alloys. However, it is found in this work that both stainless steel 310 and Incoloy 800H samples were severely corroded after 500 h immersion test at 700 °C when the alloy samples directly contacted with the over-added Mg in the liquid form. The corrosion attack is different from the classical impurity-driven corrosion in molten chloride salts found in previous work. Microscopic analysis indicates that Ni preferentially leaches out of alloy matrix due to the tendency to form MgNi2/Mg2Ni compounds. The Ni-depletion leads to the formation of a porous corrosion layer on both alloys, with the thickness around 204 µm (stainless steel 310) and 1300 µm (Incoloy 800H), respectively. These results suggest that direct contact of liquid Mg with Ni-containing alloys should be avoided during using Mg as a corrosion inhibitor for MgCl2–NaCl–KCl or other chlorides for high temperature heat storage and transfer.

关键词： concentrated solar power (CSP)     Mg corrosion inhibitor     Mg–Ni intermetallic     salt purification     thermal energy storage (TES)    

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Deep eutectic ionic liquids based on DABCO-derived quaternary ammonium salts: A promising reaction medium

Muhammad Faisal, Azeem Haider, Quret ul Aein, Aamer Saeed, Fayaz Ali Larik

《化学科学与工程前沿（英文）》 2019年 第13卷 第3期   页码 586-598 doi: 10.1007/s11705-018-1788-6

摘要： Owing to the directional H-bonding, coordination and -stacking abilities, terpyridines have been widely used as supramolecular tectons in molecular architectures, skeletons in molecular devices and metallopolymers, and are gaining importance in medicinal chemistry. In this paper, we have synthesized, characterized and applied deep eutectic ionic liquids (DEILs) based on 1,4-diazabicyclo[2.2.2]octane; triethylenediamine (DABCO)-derived quaternary ammonium salts for the preparation of terpyridines. These DEILs were synthesized through -alkylation of DABCO with haloalkanes (1-bromopentane or 1-bromoheptane) followed by mixing and heating with methanol or polyethylene glycol as a hydrogen bond donor. The synthesized DEILs were structurally characterized by IR and NMR. The formation of deep eutectic solvent was confirmed by freezing point depression, it composition was investigated through phase diagram, and its thermal stability was determined through differential scanning calorimetry, derivative thermogravimetry and thermal gravimetric analysis studies. Further, theseDEILswereinvestigatedfor theireffectivenesstowards synthesis of 2,2′:6′,2″-terpyridine, 3,2′:6′,3″-terpyridineand 4,2′:6′,4″-terpyridinederivatives through Kröhnke reaction. The results show that these three types of terpyridines can be obtained in reasonable yields (80% 97%) by the one-pot reaction of 2-, 3- or 4-acetylpyridine with a variety of aromatic aldehydes in the presence of DEIL as a reaction medium, sodium hydroxide as a base and ammonium acetate as a cyclizing agent. This methodology is highly efficient and cost-effective for synthesis of symmetrical as well as unsymmetrical terpyridines. Importantly, these DEILs can be reused several times without an obvious loss of activity and are non-toxic, low-volatile, biodegradable and highly thermally stable. Therefore, these DEILs as a non-conventional reaction medium for the synthesis of terpyridines provides appealing opportunities to be investigated in the domain of green synthesis.

关键词： terpyridine     deep eutectic solvent     ionic liquid     Kröhnke reaction     DABCO    

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标题 作者 时间 类型 操作

Corrosion behavior of metallic alloys in molten chloride salts for thermal energy storage in concentrated

Wenjin Ding, Alexander Bonk, Thomas Bauer

期刊论文

Effects of additive NaI on electrodeposition of Al coatings in AlCl

Tianyu Yao, Haiyan Yang, Kui Wang, Haiyan Jiang, Xiao-Bo Chen, Hezhou Liu, Qudong Wang, Wenjiang Ding

期刊论文

Thermal defluorination behaviors of PFOS, PFOA and PFBS during regeneration of activated carbon by molten

期刊论文

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration

Shenghui Zhou, Kuiyi You, Zhengming Yi, Pingle Liu, Hean Luo

期刊论文

Dynamic characteristics of molten droplets and hot particles falling in liquid pool

Liangxing LI, Weimin MA, Huixiong LI, Tingkuan CHEN,

期刊论文

Analysis of molten metal spreading and solidification behaviors utilizing moving particle full-implicit

期刊论文

Phenomena identification and ranking table exercise for thorium based molten salt reactor-solid fuel

Xiaojing LIU, Qi WANG, Zhaozhong HE, Kun CHEN, Xu CHENG

期刊论文

Multi-objective optimization of molten carbonate fuel cell system for reducing CO

Ramin ROSHANDEL,Majid ASTANEH,Farzin GOLZAR

期刊论文

A new regeneration approach to cation resins with aluminum salts: application of desalination by its

Zhigang LIU, Shaomin ZHU, Yansheng LI

期刊论文

钍基熔盐堆材料发展战略

周兴泰,李志军,陆燕玲,黄鹤飞,贺周同,戴志敏,徐洪杰

期刊论文

Estimation of thermodynamic properties of the ternary molten salt system, LiF-NaF-BeF2, by the modified

ZHANG Dalin, QIU Suizheng, SU Guanghui, JIA Dounan

期刊论文

循环热载体无烟燃烧技术的试验研究

何方,王华,戴永年

期刊论文

Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NO

Biwu CHU, Jiming HAO, Junhua LI, Hideto TAKEKAWA, Kun WANG, Jingkun JIANG

期刊论文

Corrosion behavior of Fe–Cr–Ni based alloys exposed to molten MgCl2–KCl–NaCl salt with over-added

期刊论文

Deep eutectic ionic liquids based on DABCO-derived quaternary ammonium salts: A promising reaction medium

Muhammad Faisal, Azeem Haider, Quret ul Aein, Aamer Saeed, Fayaz Ali Larik

期刊论文