Please wait a minute...
中国腐蚀与防护学报  2026, Vol. 46 Issue (3): 693-702     CSTR: 32134.14.1005.4537.2025.295      DOI: 10.11902/1005.4537.2025.295
  研究报告 本期目录 | 过刊浏览 |
Q345R碳钢在Hitec高温熔盐中动态腐蚀特性实验对比研究
魏旭光1, 王维斌2, 李康2, 张灿灿1(), 吴玉庭1, 鹿院卫1, 王国强1, 赵博3
1.北京工业大学 传热与能源利用北京市重点实验室 国家能源用户侧储能创新研发中心 北京 100124
2.国家管网集团科学技术研究总院分公司 天津 300457
3.中国特种设备检测研究院 北京 100029
Dynamic Corrosion Behavior of Q345R Carbon Steel in High-temperature Hitec Molten Salt
WEI Xuguang1, WANG Weibin2, LI Kang2, ZHANG Cancan1(), WU Yuting1, LU Yuanwei1, WANG Guoqiang1, ZHAO Bo3
1.Beijing Key Laboratory of Heat Transfer and Energy Conversion, National User-Side Energy Storage Innovation Research and Development Center, Beijing University of Technology, Beijing 100124, China
2.PipeChina Institute of Science and Technology, Tianjin 300457, China
3.China Special Equipment Inspection and Research Institute Beijing, Beijing 100029, China
引用本文:

魏旭光, 王维斌, 李康, 张灿灿, 吴玉庭, 鹿院卫, 王国强, 赵博. Q345R碳钢在Hitec高温熔盐中动态腐蚀特性实验对比研究[J]. 中国腐蚀与防护学报, 2026, 46(3): 693-702.
Xuguang WEI, Weibin WANG, Kang LI, Cancan ZHANG, Yuting WU, Yuanwei LU, Guoqiang WANG, Bo ZHAO. Dynamic Corrosion Behavior of Q345R Carbon Steel in High-temperature Hitec Molten Salt[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(3): 693-702.

全文: PDF(19896 KB)   HTML
摘要: 

Hitec熔盐作为高效传热储热介质,在火电机组灵活性改造中至关重要,其与储罐结构材料Q345R碳钢的动态相容性是决定系统长期可靠性的关键科学问题。本文针对动态工况下腐蚀数据与机理缺失的现状,通过400 ℃、1000 h的动态腐蚀实验,系统阐明了3种工况下(0、1、2 m/s)对Q345R碳钢在Hitec熔盐中腐蚀动力学行为的影响规律与作用机制。定量研究结果表明,材料的年平均腐蚀速率随流速增加而显著提升,分别为18.20 μm/a (静态)、20.64 μm/a (+13.5%)及21.82 μm/a (+19.93%),建立了该材料体系下腐蚀速率与流速的定量耦合关系。微观结构表征揭示,尽管不同流速条件下的腐蚀产物相组成相同(Fe2O3, Fe3O4, FeCr2O4),但其形成与演化机制存在本质差异:动态冲刷不仅机械破坏表面氧化层的完整性,导致保护性失效与加速剥落,更显著促进了腐蚀性介质(如氧)向基体内部迁移及关键合金元素Cr的选择性溶出,从而协同加剧了腐蚀进程。本研究从动力学与微观机理层面,构建了Q345R碳钢初期保护性氧化膜形成、中期冲刷主导的膜层破坏与内氧化竞争、后期元素迁移与贫化主导的内腐蚀发展的失效物理模型,为高可靠性熔盐储罐的设计与安全评价提供了理论依据与数据支撑。

关键词 熔盐储热动态腐蚀碳钢    
Abstract

The so called Hitec molten salt (40%NaNO2-7%NaNO3-53%KNO3, by mass fraction), as an efficient heat transfer and thermal storage medium, plays a crucial role in the flexibility retrofitting of thermal power plants. The dynamic compatibility between this medium and the storage tank structural material, Q345R carbon steel, constitutes a key scientific issue determining the long-term reliability of the system. Addressing the current lack of corrosion data and mechanistic understanding under dynamic conditions, herein, the influence of flow velocity (0-2 m/s) of the salt on the corrosion kinetics and underlying mechanisms of Q345R carbon steel in Hitec molten salt at 400 ℃ for 1000 h was assessed. Quantitative results demonstrate that the average annual corrosion rate of the steel increases significantly with the increasing flow velocity, namely from 18.20 μm/a for static state increases to 20.64 μm/a and 21.82 μm/a for 1 and 2 m/s, corresponding to increment of 13.5% and 19.93%, respectively. Then a quantitative correlation between the corrosion rate and the flow velocity of salt was established for this material system. Microstructural characterization revealed that although the phase composition of the corrosion products was consistent across different flow velocities (namely Fe2O3, Fe3O4, FeCr2O4), however, their formation and evolution mechanisms differ fundamentally. Dynamic flow not only mechanically compromises the integrity of the surface oxide scale, leading to protective function loss and accelerated spallation, but also significantly enhances the inward migration of corrosive species (e.g., oxygen) and the selective dissolution of the key alloying element Cr, synergistically exacerbating the corrosion process. From the perspectives of kinetics and micro-mechanisms, a comprehensive failure model for Q345R carbon steel was also proposed as follows: the initial protective oxide formation, intermediate flow-dominated oxide scale degradation competing with internal oxidation, and late-stage inward migration and depletion-dominated internal corrosion development. In sum, the findings may provide good reference for the design and safety assessment of highly reliable molten salt storage tanks.

Key wordsmolten salt    thermal energy storage    dynamic corrosion    carbon steel
收稿日期: 2025-09-16      32134.14.1005.4537.2025.295
ZTFLH:  TG174  
基金资助:国家重点研发计划(2025YFE0118800);北京市自然科学基金(L259010);国家市场监督管理总局重点实验室开发基金(SYS-TZSBAQYJJ-2025-004)
通讯作者: 张灿灿,E-mail:zcc@bjut.edu.cn,研究方向为熔盐储能及太阳能热利用
Corresponding author: ZHANG Cancan, E-mail: zcc@bjut.edu.cn
作者简介: 魏旭光,男,2000年生,硕士生
图1  动态腐蚀装置实验系统结构示意图
图2  Q345R碳钢腐蚀失重mmass随时间变化曲线图与平均腐蚀速率Rdepth随时间变化柱状图
图3  Q345R碳钢在0 m/s下腐蚀300、500、700和1000 h的表面形貌
图4  Q345R碳钢在1000 h时流速为0、1、2 m/s的表面形貌
图5  Q345R碳钢在400 ℃下流速为0、1、2 m/s Hitec熔盐中腐蚀1000 h后横截面的SEM形貌及相应的元素面分布图
图6  Q345R碳钢在400 ℃下流速为0和2 m/s Hitec熔盐中腐蚀1000 h后横截面的EDS映射图
图7  Q345R碳钢在2 m/s中腐蚀不同时间下的XRD图
图8  Q345R碳钢腐蚀1000 h后的XRD图
图9  Q345R 碳钢在不同熔盐流动条件下的腐蚀机理示意图
[1] Zuo Y, Cao M P, Shen M, et al. Effect of mg on corrosion of 316H stainless steel in molten salts MgCl2-NaCl-KCl [J]. J. Chin. Soc. Corros. Prot., 2021, 41: 80
[1] 左 勇, 曹明鹏, 申 淼 等. MgCl2-NaCl-KCl熔盐体系中金属Mg对316H不锈钢的缓蚀性能研究 [J]. 中国腐蚀与防护学报, 2021, 41: 80
[2] Wang Y Y, Lu Y W, He C, et al. Screening and thermophysical properties study of mixed molten salts with same cation [J]. J. Eng. Thermophys., 2025, 46: 1640
[2] 王元媛, 鹿院卫, 何 聪 等. 相同阳离子混合熔盐筛选及热物性研究 [J]. 工程热物理学报, 2025, 46: 1640
[3] Zeng C L, Zhang J Q, Wu W T. Monitoring of cracking of oxide film during hot corrosion [J]. J. Chin. Soc. Corros. Prot., 1993, 13: 59
[3] 曾潮流, 张鉴清, 吴维㞵. 熔盐腐蚀过程中氧化膜破裂的监测 [J]. 中国腐蚀与防护学报, 1993, 13: 59
[4] Peng Q, Wei X L, Ding J, et al. High-temperature thermal stability of molten salt materials [J]. Int. J. Energy Res., 2008, 32: 1164
doi: 10.1002/er.v32:12
[5] Sandoval-Amador A, Santander-Vega A J, Amaya-Cáceres C C, et al. 316L stainless steel corrosion in molten salts NaNO3 KNO3 NaNO2 simulating storage conditions [J]. J. Phys.: Conf. Ser., 2019, 1159: 012011
[6] Fernández A G, Galleguillos H, Fuentealba E, et al. Corrosion of stainless steels and low-Cr steel in molten Ca(NO3)2-NaNO3-KNO3 eutectic salt for direct energy storage in CSP plants [J]. Sol. Energy Mater. Sol. Cells, 2015, 141: 7
doi: 10.1016/j.solmat.2015.05.004
[7] Fernández A G, Cortes M, Fuentealba E, et al. Corrosion properties of a ternary nitrate/nitrite molten salt in concentrated solar technology [J]. Renew. Energy, 2015, 80: 177
doi: 10.1016/j.renene.2015.01.072
[8] Xiao Y, Ding L L, Liao W J, et al. Corrosion resistances of 304, 316L and 321 austenite stainless steel in nitrate molten salt [J]. Mater. Rep., 2016, 30: 217
[8] 肖 扬, 丁柳柳, 廖文俊 等. 奥氏体不锈钢304、316L和321在熔融硝酸盐中的耐腐蚀性 [J]. 材料导报, 2016, 30: 217
[9] Ahmed O. Corrosion behaviour of AISI 304 stainless steel in contact with eutectic salt for concentrated solar power plant applications [D]. Florida: University of Central Florida, 2013
[10] Kramer C M, Smyrl W H, Estill W B. Corrosion of Fe alloys in NaNO3-KNO3-NaNO2 at 823 K [J]. J. Mater. Energy Syst., 1980, 1: 59
doi: 10.1007/BF02833362
[11] Federsel K, Wortmann J, Ladenberger M. High-temperature and corrosion behavior of nitrate nitrite molten salt mixtures regarding their application in concentrating solar power plants [J]. Energy Procedia, 2015, 69: 618
doi: 10.1016/j.egypro.2015.03.071
[12] Liu H W, Xiong F P, Lv Y L, et al. CO2 corrosion inhibition of carbon steel by dodecylamine under flow conditions [J]. J. Chin. Soc. Corros. Prot., 2016, 36: 645
[12] 刘宏伟, 熊福平, 吕亚林 等. 动态条件下十二胺对Q235碳钢CO2腐蚀的缓蚀行为研究 [J]. 中国腐蚀与防护学报, 2016, 36: 645
doi: 10.11902/1005.4537.2016.121
[13] Wang X, Liu F, Li Y, et al. Corrosion behavior of B10 Cu-Ni alloy pipe in static and dynamic seawater [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 119
[13] 王 晓, 刘 峰, 李 焰 等. 静态和动态海水中B10铜镍合金管的腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2023, 43: 119
[14] Liu G Q, Zheng Y G, Jiang S L, et al. Stability and erosion corrosion behavior of corrosion product film of Q235 carbon steel and Cr5Mo low alloy steel in simulated oil refinery media [J]. J. Chin. Soc. Corros. Prot., 2015, 35: 122
[14] 刘贵群, 郑玉贵, 姜胜利 等. 模拟炼油环境中Q235钢和Cr5Mo钢表面硫化物膜稳定性及动态冲刷腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2015, 35: 122
[15] Han X L, Lu Y W, Ma Y C, aler. Research on the dynamic corrosion characteristics of ternary nitrocarbonate acid mixed molten salt at high decomposition temperatures [J]. Energy Storage Sci. Technol., 2025, 14: 1386
[15] 韩昕龙, 鹿院卫, 马彦成 等. 三元硝基碳酸高分解温度混合熔融盐动态腐蚀特性 [J]. 储能科学与技术, 2025, 14: 1386
doi: 10.19799/j.cnki.2095-4239.2024.1057
[16] García-Martín G, Lasanta M I, Encinas-Sánchez V, et al. Evaluation of corrosion resistance of A516 steel in a Molten nitrate salt mixture using a pilot plant facility for application in CSP plants [J]. Sol. Energy Mater. Sol. Cells, 2017, 161: 226
doi: 10.1016/j.solmat.2016.12.002
[17] Ma L N, Wu Y T, Zhang C C, et al. Dynamic corrosion behaviors of autennitic stainless steel in quaternary nitrate-niotrite molten salt [J]. Acta Energ. Sol. Sin., 2023, 44: 497
[17] 马丽娜, 吴玉庭, 张灿灿 等. 奥氏体不锈钢在四元硝酸盐中的动态腐蚀行为研究 [J]. 太阳能学报, 2023, 44: 497
doi: 10.19912/j.0254-0096.tynxb.2021-1286
[18] Chen L J, Hu J Y, Zhong X K, et al. Corrosion behaviors of Q345R steel at the initial stage in an oxygen-containing aqueous environment: Experiment and modeling [J]. Materials, 2018, 11: 1462
doi: 10.3390/ma11081462
[19] Xie Y, Chen X, Wu Y T, et al. Experimental study on the stress corrosion behavior of Q345R and 20# carbon steels in low-temperature ternary salts [J]. J. Energy Storage, 2025, 135:118404
doi: 10.1016/j.est.2025.118404
[20] Ou G F, Qian G W, Jin H Z, et al. Microstructure and corrosion resistance of fusion welding zone for duplextubes welded with Q345R tube sheet under different welding currents [J]. Metals, 2022, 12: 705
doi: 10.3390/met12050705
[21] Liu X F, Li R, Yao H C, et al. Research on the corrosion mechanism of Q345R steel under water-oil two-phase flow with the HCl and NH4Cl corrosive medium in low-temperature system of petrochemical plants [J]. Colloids Surf., 2024, 703A: 135360
[22] Zhang H, Jiang L, Cen Z B, et al. On corrosion and fatigue resistance of pressure vessel steel Q345R after laser shock repair [J]. Explos. Shock Waves, 2022, 42: 103101
[22] 张 浩, 蒋 磊, 岑志波 等. 激光冲击修复后压力容器钢Q345R耐腐蚀及抗疲劳性能研究 [J]. 爆炸与冲击, 2022, 42: 103101
[23] State Administration for Market Regulation, Standardization Administration of the People's Republic of China. Technical requirements for thermal energy storage media and heat transfer fluid of solar thermal power plants—Molten salt [S]. Beijing: Standards Press of China, 2024
[23] 国家市场监督管理总局, 国家标准化管理委员会. 太阳能光热发电站储热/传热用工作介质技术要求 熔融盐 [S]. 北京: 中国标准出版社, 2024
[24] State Administration for Market Regulation, Standardization Administration of the People's Republic of China. Technical requirements for molten salt thermal storage system of solar thermal electric plant [S]. Beijing: Standards Press of China, 2025
[24] 国家市场监督管理总局, 国家标准化管理委员会. 太阳能光热发电站熔融盐储热系统技术要求 [S]. 北京: 中国标准出版社, 2025
[25] Ma L N, Zhang C C, Wu Y T, et al. Dynamic corrosion behavior of 316L stainless steel in quaternary nitrate-nitrite salts under different flow rates [J]. Sol. Energy Mater. Sol. Cells, 2020, 218: 110821
doi: 10.1016/j.solmat.2020.110821
[26] Wan M Z, Wang J L, Chen Y A, et al. Compatibility of low-temperature mixed nitrate and Q345R storage tank material [J]. Energy Storage Sci. Technol., 2023, 12: 3099
[26] 万明忠, 王金龙, 陈永安 等. 低温混合硝酸盐与储罐材料Q345R相容性研究 [J]. 储能科学与技术, 2023, 12: 3099
doi: 10.19799/j.cnki.2095-4239.2023.0443
[27] Gao Q, Lu Y W, Yu Q, et al. High-temperature corrosion behavior of austenitic stainless steel in quaternary nitrate molten salt nanofluids for concentrated solar power [J]. Sol. Energy Mater. Sol. Cells, 2022, 245: 111851
doi: 10.1016/j.solmat.2022.111851
[28] Zhang X M, Zhang C C, Wu Y T, et al. Experimental research of high temperature dynamic corrosion characteristic of stainless steels in nitrate eutectic molten salt [J]. Sol. Energy, 2020, 209: 618
doi: 10.1016/j.solener.2020.09.034
[1] 卢华轶, 李若愚, 程宇飞, 白英雄, 王艳丽. NiCrMoNbNiCoFeCrMoNb合金在700 ℃熔融NaCl-KCl-MgCl2 中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2026, 46(3): 730-742.
[2] 汪崧, 刘学武, 赵健, 李众, 杨吉可. 金银花植物提取物作为环保型缓蚀剂对低碳钢酸性溶液腐蚀的缓蚀效果[J]. 中国腐蚀与防护学报, 2026, 46(2): 541-548.
[3] 胡宗武, 刘建国, 王钰, 李楷. 含砂3.5%NaCl溶液中90°弯管冲刷腐蚀损伤机制研究[J]. 中国腐蚀与防护学报, 2026, 46(2): 611-619.
[4] 岳远广, 尹志彪, 张子月, 江社明, 张启富. 一种大气腐蚀实时监测装置的开发及其在不同环境中的应用[J]. 中国腐蚀与防护学报, 2026, 46(1): 308-314.
[5] 李兆南, 侯禹岑, 莒鹏, 庄铁钢, 陈景杰, 王明昱, 徐云泽. 模拟液滴电导率变化对碳钢大气腐蚀的影响机制研究[J]. 中国腐蚀与防护学报, 2025, 45(6): 1537-1548.
[6] 王得, 张璠, 王兴奇, 张贺新, 赵成志, 杨延格. 单组分氟碳改性环氧涂层对碳钢和铝合金长期防腐性能的对比研究[J]. 中国腐蚀与防护学报, 2025, 45(6): 1549-1562.
[7] 彭立园, 谢敬礼, 曹胜飞, 谭季波, 吴欣强, 张兹瑜. 日本高放废物处置容器腐蚀厚度设计研究进展[J]. 中国腐蚀与防护学报, 2025, 45(3): 563-576.
[8] 王昆, 邹兰欣, 郭磊, 闫凯, 叶福兴, 刘洪丽, 郭洪波. 航空发动机及燃气轮机热障涂层高温腐蚀与防护[J]. 中国腐蚀与防护学报, 2025, 45(1): 1-19.
[9] 杜鑫, 杜乾, 苏钲雄, 郭少强, 王盛. 裂变产物碲致高镍合金GH3535晶间腐蚀研究[J]. 中国腐蚀与防护学报, 2024, 44(5): 1157-1163.
[10] 王刚, 李昭, 王涛, 段腾, 杜翠薇. 光伏桩基用钢在新疆土壤中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2024, 44(4): 987-992.
[11] 王长罡, DANIEL Enobong Felix, 李超, 董俊华, 杨华, 张东玖. 海洋环境中碳钢和不锈钢螺栓紧固件的腐蚀机制差异研究[J]. 中国腐蚀与防护学报, 2023, 43(4): 737-745.
[12] 郝文魁, 陈新, 徐玲铃, 韩钰, 陈云, 黄路遥, 祝志祥, 杨丙坤, 王晓芳, 张强. 电网碳钢、镀锌钢大气腐蚀等级图绘制研究[J]. 中国腐蚀与防护学报, 2023, 43(4): 795-802.
[13] 邹文杰, 丁立, 张雪姣, 陈均. 环氧树脂/有机硅氧烷改性阳离子丙烯酸乳液复合涂层的研究[J]. 中国腐蚀与防护学报, 2023, 43(4): 922-928.
[14] 夏晓健, 万芯媛, 陈云翔, 韩纪层, 陈奕扬, 严康骅, 林德源, 陈天鹏, 左晓梅, 孙宝壮, 程学群. 两种热处理工艺对3Cr钢腐蚀行为影响及机理研究[J]. 中国腐蚀与防护学报, 2023, 43(3): 656-662.
[15] 申聚宝, 崔宇, 刘莉, 刘叡, 孟凡帝, 王福会. DZ40M和K452高温合金在NaCl熔盐中的循环热腐蚀行为研究[J]. 中国腐蚀与防护学报, 2023, 43(2): 280-288.