Ni-Cr合金在富CO2 气氛中的高温腐蚀研究进展

doi:10.11900/0412.1961.2023.00498

金属学报

2024, Vol. 60

Issue (6): 731-742 DOI: 10.11900/0412.1961.2023.00498

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Ni-Cr合金在富CO₂ 气氛中的高温腐蚀研究进展

谢云¹(

), Zhang Jianqiang², 彭晓¹

1 南昌航空大学材料科学与工程学院南昌 330063
2 School of Materials Science and Engineering, University of New South Wales, Sydney 2052, Australia

Research Advances in High Temperature Corrosion of Ni-Cr Alloys in CO₂-Rich Environments

XIE Yun¹(

), Zhang Jianqiang², PENG Xiao¹

1 School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China
2 School of Materials Science and Engineering, University of New South Wales, Sydney 2052, Australia

引用本文:

谢云, Zhang Jianqiang, 彭晓. Ni-Cr合金在富CO₂ 气氛中的高温腐蚀研究进展[J]. 金属学报, 2024, 60(6): 731-742.
Yun XIE, Jianqiang Zhang, Xiao PENG. Research Advances in High Temperature Corrosion of Ni-Cr Alloys in CO₂-Rich Environments[J]. Acta Metall Sin, 2024, 60(6): 731-742.

全文: PDF(1930 KB) HTML

摘要:

发展富氧燃烧技术和提高锅炉的蒸汽参数可以有效减少燃煤电厂的CO₂排放，有助于火力发电行业实现“碳达峰-碳中和”的目标，但采用上述技术对锅炉材料的抗CO₂高温腐蚀性能和高温蠕变强度提出了更高要求，镍基合金有望成为优选材料。针对先进超超临界发电机组富氧燃烧烟气高含CO₂的特点，本文综述了目前关于Ni-Cr合金在富CO₂气氛中的高温腐蚀研究成果，重点介绍了CO₂气氛对Ni-Cr合金热生长Cr₂O₃保护膜的影响，阐明了Ni-Cr合金在CO₂气氛中发生碳化的机理，总结了富CO₂气氛中的H₂O(g)、SO₂、环境温度和合金元素对Ni-Cr合金抗高温腐蚀性能的影响，进而提出未来关于Ni-Cr合金在富CO₂气氛中的高温腐蚀需深入研究的问题，包括：解析Ni-Cr合金在不同气氛中热生长Cr₂O₃膜的微观精细结构，探明CO₂、H₂O(g)和SO₂与稀土元素在氧化膜晶界处的交互作用，关注富CO₂气氛中的HCl(g)组分对Ni-Cr合金形成Cr₂O₃保护膜的影响。

关键词 ： Ni-Cr合金, 富CO₂气氛, 高温腐蚀

Abstract：

The thermal power generation industry in China is facing heavy pressure from environmental protection sectors as the “emission peak-carbon neutrality” goal has been proposed. Oxyfuel combustion and operating with high steam parameters are considered promising technologies that can effectively reduce CO₂ emissions from coal-fired power plants. However, using these two technologies, the currently used ferritic/martensitic heat-resistant steels and austenitic stainless steels in traditional boilers cannot meet the requirements of good creep strength and corrosion resistance to hot CO₂-rich gasses. Thus, nickel-based alloys must be considered. Given that flue gasses related to oxyfuel combustion are characterized by high CO₂ concentrations, this work reviews recent research progress on the high-temperature corrosion of Ni-Cr alloys in CO₂-rich gasses. Herein, the effect of CO₂ on protective Cr₂O₃ scale formation is introduced, and the related carburization mechanism caused by CO₂ ingress is clarified. Moreover, the impacts of H₂O(g), SO₂, temperature, and alloying elements on the high temperature resistance of Ni-Cr alloys in CO₂-rich gasses are summarized. Based on the current findings, future research on high-temperature corrosion of Ni-Cr alloys in CO₂-rich gases should focus on the following key points, such as analyzing the microstructure of Cr₂O₃ scales formed in different gasses; elucidating the interaction of CO₂, H₂O(g), and SO₂ molecules with rare earth elements at grain boundaries of oxide scales; and investigating the effect of HCl(g) impurities in CO₂-rich gasses on Cr₂O₃ scaling of Ni-Cr alloys.

Key words： Ni-Cr alloy CO₂-rich environment high temperature corrosion

收稿日期: 2023-12-27

ZTFLH:

TG172.8

基金资助:国家自然科学基金项目(52301089);江西省重点研发计划项目(20232BBE50007);江西省自然科学基金项目(20224BAB214018)

通讯作者: 谢云，yun.xie@nchu.edu.cn，主要从事金属材料高温腐蚀的研究;

Corresponding author: XIE Yun, associate professor, Tel: 15827996962, E-mail: yun.xie@nchu.edu.cn

作者简介: 谢云，男，1988年生，副教授，博士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2023.00498 或 https://www.ams.org.cn/CN/Y2024/V60/I6/731

图1 Ni-30Cr合金在650℃下Ar + 20O2和Ar + 20CO2 (体积分数，%)气氛中腐蚀310 h后的截面SEM像[36,37]

图2 Ni-25Cr和Ni-30Cr合金在700℃下Ar + 20CO2气氛中腐蚀500 h后晶界碳化物的SEM像[37]

图3 Fe-20Cr合金先后在650℃下Ar + 20O2和Ar + 20CO2气氛中腐蚀所形成Cr2O3膜的三维原子探针像[60]

图4 Ni-15Cr合金和纯Ni在650℃下Ar + 20CO2和Ar + 20CO2 + 20H2O气氛中腐蚀后的截面SEM像[42]

图5 Ni-30Cr合金在800℃下Ar + 20CO2 + 20H2O和Ar + 20CO2气氛中腐蚀500 h后的截面SEM像和TEM像[75]

T / ^oC	$D ˜ C r$ / (cm²·s^-1)	$N C r (1)$	$N C r (2)$
650	2.6 × 10^-15	0.31	> 0.68
700	1.4 × 10^-14	0.28	0.39
800	2.3 × 10^-13	0.24	0.16

图6 Ni-25Cr合金在不同温度下Ar + 20CO2气氛中腐蚀500 h后的截面SEM像[37]

图7 Ni-30Cr-2Ti合金在700℃下Ar + 20CO2 + 20H2O气氛中腐蚀不同时间后的碳化物SEM像[73]

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