镍基合金在含侵蚀性离子的超临界水氧化中的腐蚀研究进展

doi:10.16085/j.issn.1000-6613.2024-0604

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 2141-2155.DOI: 10.16085/j.issn.1000-6613.2024-0604

镍基合金在含侵蚀性离子的超临界水氧化中的腐蚀研究进展

陈积权¹(), 任鹏炜², 朱日广³, 陈思思¹, 唐兴颖³(), 覃新宇⁴(), 杨健乔⁵

^1.广西大学资源环境与材料学院，广西南宁 530004
^2.中国检验认证集团广西有限公司，广西南宁 538001
^3.广西大学海洋学院，广西南宁 530004
^4.广西绿色低碳技术研究院有限公司，广西南宁 530004
^5.西安交通大学能源与动力学院，陕西西安 710049

收稿日期:2024-04-10 修回日期:2024-05-20 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 唐兴颖,覃新宇
作者简介:陈积权（2000—），男，硕士研究生，研究方向为超临界水氧化防腐材料。E-mail：2215393002@st.gxu.edu.cn。
基金资助:
国家自然科学基金(22068003)

Corrosion of nickel-based alloys in supercritical water oxidation containing erosive ions: A review

CHEN Jiquan¹(), REN Pengwei², ZHU Riguang³, CHEN Sisi¹, TANG Xingying³(), QIN Xinyu⁴(), YANG Jianqiao⁵

^1.School of Resources, Environment and Materials, Guangxi University, Nanning 530004, Guangxi, China
^2.China Certificationn and Inspectio Group Guangxi Co. , Ltd. , Nanning 538001, Guangxi, China
^3.School of Marine Sciences, Guangxi University, Nanning 530004, Guangxi, China
^4.Guangxi Institute of Green and Low Carbon Technology Co. , Ltd. , Nanning 530004, Guangxi, China
^5.School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China

Received:2024-04-10 Revised:2024-05-20 Online:2025-04-25 Published:2025-05-07
Contact: TANG Xingying, QIN Xinyu

摘要/Abstract

摘要：

超临界水氧化（SCWO）技术是一种高效环保的高级氧化技术，被广泛应用于处理各种高浓度污染物，但在处理过程中会产生酸性物质导致设备腐蚀，严重限制了SCWO的发展。镍基合金具有优异的高温强度、抗氧化和抗腐蚀性能，是制备超临界水氧化设备的候选材料之一，探究其在SCWO中的腐蚀现象和机理对技术的发展具有重要的意义。本文回顾了在含不同侵蚀性离子（O^2-、Cl^-、S^2-、PO $4 3 -$ 等）的超临界水环境中镍基合金的腐蚀情况，总结了不同侵蚀性离子对腐蚀的影响。对比发现，在含Cl或S的环境下对合金的腐蚀影响更大。详细讨论不同的侵蚀性离子在超临界水中对镍基合金的腐蚀机理，并提出涂层和表面改性两种减缓腐蚀的方法。最后，对合金腐蚀的未来发展方向进行了展望，提出使用同位素标记和纯金属腐蚀两种方法深入剖析阐明合金在超临界水氧化环境中的腐蚀机理。

关键词: 超临界水氧化, 镍基合金, 侵蚀性离子, 腐蚀机理, 高效环保

Abstract:

Supercritical water oxidation (SCWO) is a highly efficient and environmentally friendly advanced oxidation technology, which is widely used to treat a variety of high-concentration pollutants, but acidic substances are generated during the treatment process, leading to corrosion of the equipment, which seriously limits the development of SCWO. Ni-based alloys with excellent high-temperature strength, oxidation and corrosion resistance are one of the candidate materials for the preparation of SCWO equipment, and it is of great significance for the development of the technology to investigate the corrosion phenomena and mechanisms in SCWO. This paper reviewed the corrosion of Ni-based alloys in supercritical water environment containing different aggressive ions (O^2-、Cl^-、S^2-、PO $4 3 -$ , etc.), and summarized the effect of different aggressive ions on corrosion. It was found that the corrosion of the alloy was more affected in the environment containing Cl or S. The corrosion mechanism of Ni-based alloys in supercritical water by different aggressive ions was discussed in detail, and two methods to slow down the corrosion by coating and surface modification were proposed. Finally, the future development direction of alloy corrosion was discussed, and it was proposed to use isotope labeling and pure metal corrosion to deeply analyze and elucidate the corrosion mechanism of alloys in the oxidizing environment of supercritical water.

Key words: supercritical water oxidation, Ni-based alloys, erosive ions, corrosion mechanism, highly efficient and environmental friendly

中图分类号:

TG17

陈积权, 任鹏炜, 朱日广, 陈思思, 唐兴颖, 覃新宇, 杨健乔. 镍基合金在含侵蚀性离子的超临界水氧化中的腐蚀研究进展[J]. 化工进展, 2025, 44(4): 2141-2155.

CHEN Jiquan, REN Pengwei, ZHU Riguang, CHEN Sisi, TANG Xingying, QIN Xinyu, YANG Jianqiao. Corrosion of nickel-based alloys in supercritical water oxidation containing erosive ions: A review[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2141-2155.

图/表 11

图1 合金800H在SCW中的扫描电子显微镜（SEM）图[25]

图2 在超临界氨/氯化铵溶液实验后的镍基合金和钴基合金SEM图[32]

图3 含5000μL/L硫化物的SCW中的C276试样的横截面后向散射电子图像以及腐蚀层能量色散X射线谱（EDS）线扫描剖面[41]

图4 在含3600mg/L磷酸盐的SCW中腐蚀后的316 SS、C276和TA 10对磷酸盐的X射线光电子能谱（XPS）和SEM图[44]

图5 合金600在含有多种无机盐（Cl-、SO42-和PO43-）的氧化性超临界水体系中的腐蚀机理示意图[43]

表1 侵蚀性离子在SCW中对镍基合金腐蚀的影响

侵蚀环境	侵蚀离子	侵蚀方式	现象
O	O $2 2 -$ 、O^2-、O₂^-	低浓度弱氧化	轻微局部腐蚀如点蚀、晶间腐蚀^[53-55]
O	O $2 2 -$ 、O^2-、O₂^-	高浓度强氧化	膜剥落、点蚀和SCC^[23,56]
C1、O	Cl₂、Cl^-	占据阴离子空位、活化氧化	点蚀、鼓泡、氧化膜开裂或脱落^[48,57]
Cl	Cl^-	穿透和溶解氧化膜	强点蚀、膜开裂和SCC^[33,58]
S	S^2-	产生硫化通道，产生H₂、S^2-	裂纹、膜剥落^[41,59]
S	SO $3 2 -$ 、SO $4 2 -$	膜溶解，被还原为S^2-、S	点蚀、氧化膜剥落、均匀腐蚀^[49,60]
S、O	O^2-、S^2-	硫化、氧化、膜疏松	裂纹、点蚀、膜剥落^[38,50,61]
P	PO $4 3 -$ 、HPO $4 2 -$	盐沉积、熔盐腐蚀、溶解氧化膜	钝化、晶间腐蚀、点蚀、膜脱落^[30,36]
P、O	O^2-、PO $4 3 -$	低溶解盐、氧化	局部腐蚀、钝化、晶间腐蚀^[42]
P、S、Cl、O	DO、PO $4 3 -$ 、Cl^-、SO $4 2 -$	氧化、溶解、穿透氧化膜、硫化	磷酸盐缓蚀、强局部腐蚀、膜剥落、SCC、孔蚀、晶间腐蚀^{[43-45,47,62]}

表1 侵蚀性离子在SCW中对镍基合金腐蚀的影响

侵蚀环境	侵蚀离子	侵蚀方式	现象
O	O $2 2 -$ 、O^2-、O₂^-	低浓度弱氧化	轻微局部腐蚀如点蚀、晶间腐蚀^[53-55]
O	O $2 2 -$ 、O^2-、O₂^-	高浓度强氧化	膜剥落、点蚀和SCC^[23,56]
C1、O	Cl₂、Cl^-	占据阴离子空位、活化氧化	点蚀、鼓泡、氧化膜开裂或脱落^[48,57]
Cl	Cl^-	穿透和溶解氧化膜	强点蚀、膜开裂和SCC^[33,58]
S	S^2-	产生硫化通道，产生H₂、S^2-	裂纹、膜剥落^[41,59]
S	SO $3 2 -$ 、SO $4 2 -$	膜溶解，被还原为S^2-、S	点蚀、氧化膜剥落、均匀腐蚀^[49,60]
S、O	O^2-、S^2-	硫化、氧化、膜疏松	裂纹、点蚀、膜剥落^[38,50,61]
P	PO $4 3 -$ 、HPO $4 2 -$	盐沉积、熔盐腐蚀、溶解氧化膜	钝化、晶间腐蚀、点蚀、膜脱落^[30,36]
P、O	O^2-、PO $4 3 -$	低溶解盐、氧化	局部腐蚀、钝化、晶间腐蚀^[42]
P、S、Cl、O	DO、PO $4 3 -$ 、Cl^-、SO $4 2 -$	氧化、溶解、穿透氧化膜、硫化	磷酸盐缓蚀、强局部腐蚀、膜剥落、SCC、孔蚀、晶间腐蚀^{[43-45,47,62]}

图6 镍基合金的腐蚀机理示意图

图7 镍基合金在含Cl的超临界水体系中的腐蚀机理示意图

图8 镍基合金在含硫气氛以及SO42-的超临界水体系中的腐蚀机理示意图

图9 镍基合金在含PO43-的超临界水体系中的腐蚀机理示意图

图10 NiAl/Al2O3涂层的表面SEM图和氧化膜元素分布[110]

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镍基合金在含侵蚀性离子的超临界水氧化中的腐蚀研究进展

Corrosion of nickel-based alloys in supercritical water oxidation containing erosive ions: A review

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