高氯煤烟中的氯腐蚀锅炉换热器的机理

doi:10.11901/1005.3093.2025.354

材料研究学报

2026, Vol. 40

Issue (9): 697-709 DOI: 10.11901/1005.3093.2025.354

研究论文

本期目录 | 过刊浏览

高氯煤烟中的氯腐蚀锅炉换热器的机理

郭非凡¹, 马继刚¹, 陈丽娟¹^,²(

), 谢伟智¹, 魏博¹^,²(

), 马瑞³, 安田田¹, 李奕华¹, 李新月¹

^1.新疆大学化工学院乌鲁木齐 830017
^2.新疆煤炭清洁转化与化工过程重点实验室乌鲁木齐 830017
^3.新疆大学电气工程学院乌鲁木齐 830017

Corrosion Behavior of 12Cr1MoVG Steel in a Simulated Flue Gas for High-chlorine Coal while Containing Different Forms of Chlorine

GUO Feifan¹, MA Jigang¹, CHEN Lijuan¹^,²(

), XIE Weizhi¹, WEI Bo¹^,²(

), MA Rui³, AN Tiantian¹, LI Yihua¹, LI Xinyue¹

^1.School of Chemical Engineering, Xinjiang University, Urumqi 830017, China
^2.Xinjiang Key Laboratory of Clean Coal Conversion and Chemical Processes, Urumqi 830017, China
^3.School of Electrical Engineering, Xinjiang University, Urumqi 830017, China

引用本文:

郭非凡, 马继刚, 陈丽娟, 谢伟智, 魏博, 马瑞, 安田田, 李奕华, 李新月. 高氯煤烟中的氯腐蚀锅炉换热器的机理[J]. 材料研究学报, 2026, 40(9): 697-709.
Feifan GUO, Jigang MA, Lijuan CHEN, Weizhi XIE, Bo WEI, Rui MA, Tiantian AN, Yihua LI, Xinyue LI. Corrosion Behavior of 12Cr1MoVG Steel in a Simulated Flue Gas for High-chlorine Coal while Containing Different Forms of Chlorine[J]. Chinese Journal of Materials Research, 2026, 40(9): 697-709.

全文: PDF(27904 KB) HTML

摘要:

模拟高氯煤烟气(Cl₂/HCl + CO₂ + H₂O + N₂，550 ℃/650 ℃)的多组分可控气氛，进行了其对锅炉换热器12Cr1MoVG钢的高温腐蚀实验，根据腐蚀产生的质量损失、SEM-EDS、XRD谱和热力学计算结果研究了腐蚀的机理。结果表明温度对12Cr1MoVG钢腐蚀的影响较大。温度从550 ℃提高到650 ℃，这种钢表面氧化膜的厚度增加了232.4 µm，腐蚀产生的质量损失增加了21.26 mg/cm²，钢的表面氧化膜产生了微裂纹等缺陷。在相同的条件下，Cl₂对12Cr1MoVG钢的腐蚀比HCl严重。这种钢的试样被HCl腐蚀后表面生成易挥发的FeCl₂，FeCl₂挥发产生的孔隙使HCl穿过氧化膜与金属基底发生反应，使氧化膜产生横向和纵向裂纹；而试样被Cl₂腐蚀后表面生成的FeCl₃在更低的温度挥发后产生密集的孔洞，Cl₂通过孔洞向内渗透与基底反应使表面的氧化膜严重分层和脱落。Cl₂对锅炉换热器12Cr1MoVG钢的高温腐蚀是一种自催化循环过程：HCl、Cl₂与钢反应生成易挥发的铁基氯化物(FeCl₂、FeCl₃)，这种铁基氯化物挥发后与H₂O发生氧化反应生成HCl，于是形成循环腐蚀最终使氧化膜分层脱落。Cl₂的氧化性更强，生成的易挥发腐蚀产物比HCl更多。

关键词 ：金属材料, 高温腐蚀, 氯腐蚀, 高氯煤燃烧, 12Cr1MoVG

Abstract：

The flue gas generated from combustion of high-chlorine containing coals may induce severe corrosion on boiler heat exchanger tubes due to chlorine-containing species, significantly compromising the operational safety. Herein the high-temperature corrosion behavior of boiler steel 12Cr1MoVG was investigated in flue gas containing different chlorine species. For this purpose, a high-temperature corrosion test rig was established to simulate the flue gas environment (Cl₂/HCl + CO₂ + H₂O + N₂, 550 ^oC/650 ^oC) in boilers firing high-chlorine coal while containing different forms of chlorine. The corrosion behavior of the steel was characterized by means of mass loss measurement, SEM-EDS, XRD, and thermodynamic calculations. The results revealed that temperature significantly influences material corrosion. When temperature increased from 550 ^oC to 650 ^oC, oxide scale thickness increased by 232.4 µm with a corresponding mass loss increase of 21.26 mg/cm². Microcracks developed in the surface oxide scale due to thermal stress. Under identical conditions, Cl₂ induced more severe corrosion than HCl. When the corrosion of steel in artificial flue gas containing HCl may generate volatile FeCl₂, whose sublimation created porous pathways allowing HCl penetration through the oxide scale to react with the steel substrate, simultaneously inducing transverse and longitudinal cracks. In contrast, when exposure to ones containing Cl₂ the steel corrosion could induce the formation of FeCl₃, which volatilizes at lower temperatures, producing dense porosity that facilitated inward chlorine diffusion and subsequent reaction with the steel substrate, ultimately causing severe oxide scale delamination and spallation. Chlorine-induced high-temperature corrosion of the steel follows an autocatalytic cycle: HCl/Cl₂ reacts with the steel to form volatile iron chlorides (FeCl₂/FeCl₃). These compounds volatilize and undergo oxidation with H₂O, regenerating HCl to sustain the corrosive cycle. This process ultimately leads to metallic oxide scale degradation through delamination and spallation. The stronger oxidizing capability of Cl₂ and higher volatility of its corrosion products result in more severe material degradation compared to HCl.

Key words： metallic materials high-temperature corrosion chlorine corrosion high-chlorine coal combustion 12Cr1MoVG

收稿日期: 2025-11-27

ZTFLH:

TG172

基金资助:高校青年教师科研创新能力支持项目(SRICSPYF-BS2025042);国家自然科学基金(52261022);2025年国家级大学生创新训练计划项目(202510755044)

通讯作者: 陈丽娟，副教授，ljchenxju@163.com，研究方向为过程装备结构优化，金属材料腐蚀与防护；
魏博，教授，weiboxju@163.com，研究方向为固体颗粒物燃烧与燃烧污染物控制

Corresponding author: CHEN Lijuan, Tel: 18016827217, E-mail: ljchenxju@163.com;
WEI Bo, Tel: 18703028892, E-mail: weiboxju@163.com

作者简介: 郭非凡，男，2001年生，硕士生

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	郭非凡
	马继刚
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	谢伟智
	魏博
	马瑞
	安田田
	李奕华
	李新月
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https://www.cjmr.org/CN/10.11901/1005.3093.2025.354 或 https://www.cjmr.org/CN/Y2026/V40/I9/697

表1 12Cr1MoVG钢的化学成分

图1 可控气氛高温腐蚀实验台的示意图

表2 气体的组成和实验工况

图2 12Cr1MoVG钢在550 ℃、650 ℃的N2、HCl、Cl2气氛中腐蚀100 h后的质量损失

图3 12Cr1MoVG钢在N2、HCl、Cl2气氛中不同温度腐蚀20 h和100 h后的宏观形貌

图4 12Cr1MoVG钢在N2、HCl、Cl2气氛中不同温度腐蚀100 h后的微观形貌

图5 12Cr1MoVG钢试样在N2、HCl、Cl2气氛中不同温度腐蚀100 h表面的XRD谱

图6 12Cr1MoVG钢试样在550 ℃腐蚀100 h后截面的元素分布

图7 12Cr1MoVG钢试样在650 ℃腐蚀100 h后截面的元素分布

图8 12Cr1MoVG钢试样在550 ℃腐蚀100 h后截面的线扫描图

图9 12Cr1MoVG钢试样在650 ℃下腐蚀100 h后截面的线扫描图

图10 Fe、Cr、Mn和V与H2O、HCl、Cl2及MCl x 与H2O在450 ℃~750 ℃反应的热力学参数

表3 铁、铬、锰氯化物的熔点和饱和蒸气压

图11 12Cr1MoVG钢在HCl (a)、Cl2 (b)中的高温腐蚀机理

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