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中国腐蚀与防护学报  2015, Vol. 35 Issue (3): 220-226    DOI: 10.11902/1005.4537.2014.077
  研究报告 本期目录 | 过刊浏览 |
O2浓度对钢在超临界CO2中腐蚀速率的影响
张玉成1,鞠新华1,庞晓露2,高克玮2()
2. 北京科技大学材料物理与化学系 北京 100083
Effect of O2 Concentration on Corrosion Rate of Steels in Supercritical CO2
Yucheng ZHANG1,Xinhua JU1,Xiaolu PANG2,Kewei GAO2()
1. ShouGang Research Institute of Technology, Beijing 100043, China
2. Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083, China
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摘要: 

研究了油气输送管道中常用的两种碳钢C75和X65及3种不锈钢13Cr,2205和904 L在80 ℃,12 MPa含有不同浓度O2的超临界CO2环境中的腐蚀行为。结果表明,当超临界CO2中O2浓度较低时,即使是微量O2 (1.50×10-6),也能显著地加速碳钢和13Cr不锈钢的腐蚀；在O2浓度很高时 (5.70×10-2) 出现钝化现象,与不含O2时相比,无论碳钢还是13Cr不锈钢的腐蚀速率均降低；2205和904 L不锈钢的腐蚀均不受O2浓度的影响。
关键词 ： 超临界CO2,  O2,  碳钢,  不锈钢,  腐蚀速率    
Abstract：

The carbon capture and storage (CCS) in geological reservoirs is now considered to be one of the main options for achieving deep reductions in CO2 emissions. Generally, the purity of captured CO2 is only about 95% and can contain trace gases such as O2, CO, SOx and NOx. In the presence of a water phase, these trace gases can contribute to the corrosiveness of high pressure-high temperature CO2 (supercritical CO2) systems. In this study, corrosion experiments of supercritical CO2 with various amounts of O2 were carried out to study the effect of small concentrations of O2 on the corrosion rate of two kinds of carbon steels C75 and X65 and three kinds of stainless steels 13Cr, 2205 and 904L in aqueous supercritical CO2 at 80 ℃ under 12 MPa. The decay kinetics of small starting O2 concentrations were investigated and used for the experiments with continuous replenishment of used-up O2. The results indicated that constant O2 concentrations in supercritical CO2, even trace of O2 (1.50×10-6), could enhance the corrosion rate of carbon steels tremendously (more than 100 mm/a). Under this condition, even the corrosion rate of 13Cr stainless steel obviously increased. However, surprisingly, with high O2 concentrations seemed to exhibit passivation effect and the corrosion rates for carbon steels and 13Cr stainless steel were relatively low. The 2205 and 904L stainless steels were unaffected by addition of O2 and showed high resistance (<0.01 mm/a) to the aqueous supercritical CO2 corrosion.
Key words： supercritical CO2    O2    carbon steel    stainless steel    corrosion rate
    
基金资助:北京市自然科学基金重点项目（2131004）资助
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张玉成,鞠新华,庞晓露,高克玮. O2浓度对钢在超临界CO2中腐蚀速率的影响[J]. 中国腐蚀与防护学报, 2015, 35(3): 220-226.
Yucheng ZHANG, Xinhua JU, Xiaolu PANG, Kewei GAO. Effect of O2 Concentration on Corrosion Rate of Steels in Supercritical CO2. Journal of Chinese Society for Corrosion and protection, 2015, 35(3): 220-226.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2014.077      或      https://www.jcscp.org/CN/Y2015/V35/I3/220

Steel C Si Mn P S N Cr Mo Ni Cu
C75 0.2~0.4 0.1~0.3 1.0~3.0 ≤0.01 ≤0.01 --- 0.02~0.04 0.01~0.03 0.05~0.07 ---
X65 ≤0.1 0.2~0.4 1.0~3.0 ≤0.02 ≤0.01 ≤0.01 --- --- --- ---
13Cr 0.17~0.22 0.3~0.5 0.2~0.4 ≤0.04 ≤0.04 --- 12.5~13.5 --- --- ---
2205 ≤0.03 ≤1.0 ≤2.0 ≤0.03 ≤0.02 0.08~0.20 21.0~23.0 2.5~3.5 4.5~6.5 ---
904L ≤0.02 ≤0.70 ≤2.0 ≤0.03 ≤0.015 0.04~0.15 19.0~21.0 4.0~5.0 24.0~26.0 1.0~2.0
表1  实验所用材料的化学成分
图1  初始O2浓度分别为1.37×10-3和2.69×10-3时反应釜中O2浓度随腐蚀时间的变化曲线
图2  钢在一次性注入2.69×10-3 O2的超临界CO2中腐蚀后的宏观表面形貌
O2 concentration C75 X65 13Cr 2205 904 L
1.37×10-3 8.1 8.1 0.014 ＜0.01 ＜0.01
2.69×10-3 25.0 36.2 0.01 ＜0.01 ＜0.01
表2  一次性分别注入1.37×10-3和2.69×10-3 O2时钢在超临界CO2中的腐蚀速率
图3  初始O2浓度为5.7×10-2时反应釜中O2浓度随腐蚀时间的变化曲线
图4  无氧及不同O2含量时碳钢及13Cr不锈钢在超临界CO2中的腐蚀速率
图5  手动动态注入3.50×10-4 O2的过程
图6  恒定O2浓度控制过程
图7  碳钢及13Cr不锈钢在动态注入O2条件下的腐蚀速率
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