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中国腐蚀与防护学报  2025, Vol. 45 Issue (5): 1351-1360     CSTR: 32134.14.1005.4537.2024.335      DOI: 10.11902/1005.4537.2024.335
  研究报告 本期目录 | 过刊浏览 |
CO2 压力对含杂质超临界CO2 输送管线X65钢应力腐蚀开裂敏感性的影响
程璐瑶1, 徐彦磊2, 李家玮1, 孙冲1(), 林学强1, 孙建波1
1 中国石油大学(华东)材料科学与工程学院 青岛 266580
2 中国石油天然气管道科学研究院有限公司 廊坊 065000
Effect of CO2 Pressure on Stress Corrosion Cracking Susceptibility of X65 Pipeline Steel Used for Transporting Impure Supercritical CO2
CHENG Luyao1, XU Yanlei2, LI Jiawei1, SUN Chong1(), LIN Xueqiang1, SUN Jianbo1
1 School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China
2 China Petroleum Pipeline Research Institute Co., Ltd., Langfang 065000, China
引用本文:

程璐瑶, 徐彦磊, 李家玮, 孙冲, 林学强, 孙建波. CO2 压力对含杂质超临界CO2 输送管线X65钢应力腐蚀开裂敏感性的影响[J]. 中国腐蚀与防护学报, 2025, 45(5): 1351-1360.
Luyao CHENG, Yanlei XU, Jiawei LI, Chong SUN, Xueqiang LIN, Jianbo SUN. Effect of CO2 Pressure on Stress Corrosion Cracking Susceptibility of X65 Pipeline Steel Used for Transporting Impure Supercritical CO2[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1351-1360.

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摘要: 

通过慢应变速率拉伸实验和四点弯应力腐蚀实验，结合腐蚀产物膜电化学阻抗测试和微观表征，研究了X65管线钢在低含水及含O2、H2S、SO2和NO2杂质的超临界CO2环境中的应力腐蚀行为，探讨了CO2压力变化对X65管线钢应力腐蚀开裂(SCC)敏感性的影响。结果表明：在7.5 MPa至14 MPa CO2压力范围内，X65管线钢在低含水及多种杂质共存的超临界CO2环境中具有很低的SCC敏感性，在测试周期内未发生SCC。但是，X65管线钢因受到均匀腐蚀作用会产生轻微的塑性损失，进而存在一定程度的SCC敏感性。随着CO2压力由7.5 MPa升高至14 MPa，X65管线钢的SCC敏感性呈先降低后升高的变化趋势，这与CO2压力变化引起的X65管线钢腐蚀程度不同密切相关。由于CO2压力变化可以导致X65管线钢表面沉积的液相中腐蚀性物质含量和形成的腐蚀产物膜保护性发生改变，因而在应力和含杂质CO2的耦合作用下X65管线钢的腐蚀速率随CO2压力升高呈先降低后升高的变化规律。
关键词 ： X65管线钢,  超临界CO2,  CO2压力,  应力腐蚀    
Abstract：

In this study, the stress corrosion cracking behavior of X65 pipeline steel exposed to a supercritical CO2 environment with low water content and co-existence of O2, SO2, NO2, and H2S impurities was studied by means of slow strain rate tensile test, four-point-bending stress corrosion test, electrochemical measurement and surface analysis techniques. The effect of CO2 pressure change on the susceptibility of X65 pipeline steel to stress corrosion cracking (SCC) was discussed. The results show that X65 pipeline steel has a very low SCC susceptibility within the CO2 pressure range of 7.5 MPa to 14 MPa when being exposed to supercritical CO2 environment with low water content and co-existence of multiple impurities. X65 pipeline steel does not crack under the coupling effect of stress and impurity-containing CO2 streams during the overall test duration. However, X65 pipeline steel suffers from the slight ductility loss due to the corrosion effect, thereby demonstrating a certain SCC susceptibility. The SCC susceptibility of X65 pipeline steel decreases first and then increases as the rise of CO2 pressure from 7.5 MPa to 14 MPa, which is closely associated with the difference of corrosion degree caused by CO2 pressure change. When X65 pipeline steel is exposed to supercritical CO2 environment containing impurities, the content of corrosive substances in the formed aqueous phase and the protectiveness of the corrosion product film formed on the steel surface are changed with the variation of CO2 pressure. Therefore, under the coupling effect of stress and impurity-containing CO2 streams, the corrosion rate of X65 steel decreases first and then increases with the increase of CO2 pressure.
Key words： X65 pipeline steel    supercritical CO2    CO2 pressure    stress corrosion
收稿日期: 2024-10-12      32134.14.1005.4537.2024.335
ZTFLH:  TG174  
基金资助:国家自然科学基金(52001328);中央高校基本科研业务费专项(20CX06075A)
通讯作者: 孙冲，E-mail：sunchong@upc.edu.cn，研究方向为金属腐蚀与防护
Corresponding author: SUN Chong, E-mail: sunchong@upc.edu.cn
作者简介: 程璐瑶，女，2000年生，硕士生
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https://www.jcscp.org/CN/10.11902/1005.4537.2024.335      或      https://www.jcscp.org/CN/Y2025/V45/I5/1351

图1  X65管线钢的金相组织
图2  慢应变速率拉伸试样尺寸
ConditionCO2 pressure / MPaTemperature / ºCO2 / %H2S / %NO2 / %SO2 / %H2O / %
17.5500.010.010.010.010.01
210
314
表1  慢应变速率拉伸和四点弯应力腐蚀实验条件
图3  四点弯应力腐蚀实验装置示意图
图4  不同压力下在含杂质的超临界CO2环境中X65管线钢的应力-应变曲线
图5  在含杂质超临界CO2环境中不同CO2压力下X65管线钢的断面收缩率(Ψ)和SCC敏感性因子(IΨ-SCC)
图6  在空气和不同压力的含杂质超临界CO2环境中X65管线钢的拉伸断口形貌
图7  在不同压力的含杂质超临界CO2环境中施加520 MPa应力并暴露240 h后X65管线钢的应力腐蚀速率
图8  在不同CO2压力的含杂质超临界CO2环境中应力腐蚀240 h后及去除腐蚀产物膜后X65管线钢的表面宏观形貌
图9  X65管线钢在不同CO2压力的含杂质超临界CO2环境中应力腐蚀240 h后的表面、截面SEM形貌和截面EDS面扫描分析
图10  X65管线钢在不同压力的含杂质超临界CO2环境中应力腐蚀240 h后表面腐蚀产物的Raman光谱
Chemical7.5 MPa CO210 MPa CO214 MPa CO2
substanceMass / gMass fraction / %Mass / gMass fraction / %Mass / gMass fraction / %
H2O7.000 × 10-495.6353.500 × 10-495.0271.000 × 10-394.595
CO2(aq)3.260 × 10-54.3241.860 × 10-54.9415.936 × 10-55.379
O2(aq)2.441 × 10-103.242 × 10-52.064 × 10-105.486 × 10-51.012 × 10-99.169 × 10-5
H2S(aq)8.805 × 10-91.169 × 10-34.650 × 10-91.236 × 10-31.359 × 10-81.232 × 10-3
NO2(aq)3.738 × 10-84.950 × 10-31.365 × 10-83.622 × 10-32.645 × 10-82.394 × 10-3
SO2(aq)1.936 × 10-77.224 × 10-37.954 × 10-85.455 × 10-31.863 × 10-73.948 × 10-3
H+2.329 × 10-93.093 × 10-41.019 × 10-92.708 × 10-42.585 × 10-92.343 × 10-4
HCO3-8.425 × 10-91.119 × 10-35.471 × 10-91.454 × 10-32.052 × 10-81.860 × 10-3
HS-5.952 × 10-137.902 × 10-83.586 × 10-139.529 × 10-81.222 × 10-121.107 × 10-7
HSO3-1.761 × 10-72.339 × 10-27.468 × 10-81.985 × 10-21.806 × 10-71.637 × 10-2
表2  不同CO2压力的含杂质超临界CO2环境中形成液膜中CO2及杂质组分和主要离子的质量与浓度
图11  在不同压力的含杂质超临界CO2环境中X65管线钢表面腐蚀产物膜的电化学阻抗图谱及等效电路图
CO2 pressure / MPaRs / Ω·cm2Rct / Ω·cm2Y0(Qdl) / Ω-1·cm-2·S nn(Qdl)
7.513.86349.20.0330.721
1014.04491.30.0510.858
1413.88151.40.0270.705
表3  在不同CO2压力的含杂质超临界CO2环境中X65管线钢表面腐蚀膜的EIS拟合数据
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