水含量对超临界<strong>CO<sub>2</sub></strong> 输送管道腐蚀的影响

doi:10.11902/1005.4537.2023.227

中国腐蚀与防护学报

2024, Vol. 44

Issue (3): 576-584 CSTR: 32134.14.1005.4537.2023.227 DOI: 10.11902/1005.4537.2023.227

研究报告

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水含量对超临界CO₂ 输送管道腐蚀的影响

胡丽华¹, 衣华磊¹, 杨维健², 孙冲², 孙建波²(

)

1.中海油研究总院有限责任公司北京 100028
2.中国石油大学(华东)材料科学与工程学院青岛 266580

Effect of Water Content on Corrosion Behavior of X65 Pipeline Steel in Supercritical CO₂ Fluids

HU Lihua¹, YI Hualei¹, YANG Weijian², SUN Chong², SUN Jianbo²(

)

1. CNOOC Research Institute Co., Ltd., Beijing 100028, China
2. School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China

引用本文:

胡丽华, 衣华磊, 杨维健, 孙冲, 孙建波. 水含量对超临界CO₂ 输送管道腐蚀的影响[J]. 中国腐蚀与防护学报, 2024, 44(3): 576-584.
Lihua HU, Hualei YI, Weijian YANG, Chong SUN, Jianbo SUN. Effect of Water Content on Corrosion Behavior of X65 Pipeline Steel in Supercritical CO₂ Fluids[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(3): 576-584.

全文: PDF(9094 KB) HTML

摘要:

通过模拟实验和表面分析技术等方法，对比研究有无杂质的超临界CO₂输送环境中水含量对X65管线钢腐蚀行为的影响，并探讨不同水含量环境中杂质对X65钢腐蚀的影响机理。结果表明：在超临界CO₂-H₂O环境中，即使水含量达到饱和溶解度0.4114%，X65钢也仅发生轻微腐蚀，腐蚀速率为0.0013 mm/a。在O₂、H₂S、SO₂和NO₂杂质共存的超临界CO₂-H₂O环境中，水含量由0.002%增加至0.4114%，X65钢腐蚀速率由0.0181 mm/a增加至0.2901 mm/a。杂质与杂质间交互作用显著促进腐蚀性液相形成，进而加剧X65钢的腐蚀。在低含水量环境中，X65钢腐蚀过程由杂质间反应产物控制；而在高含水量环境中，杂质和杂质间反应产物共同控制X65钢的腐蚀过程。

关键词 ： X65管线钢, 超临界CO₂, 水含量, 杂质, 腐蚀

Abstract：

CO₂ induced pipeline corrosion is one of main concerns for the safe implementation and large-scale application of Carbon Capture, Utilization and Storage (CCUS) technology. Reasonably limiting the water content in supercritical CO₂ transport environments containing multiple impurities is crucial for the corrosion control of the pipeline. Herein, the effect of water content on the corrosion behavior of X65 pipeline steel in supercritical CO₂ transport environments with/without impurities of O₂, H₂S, SO₂ and NO₂ was investigated by means of simulated corrosion test with high-temperature and high-pressured autoclave, and surface analysis technology. Concurrently, the influence mechanism of impurities on the corrosion of the steel in supercritical CO₂ transport environments with different water contents was discussed. The results show that X65 steel only undergoes slight corrosion in supercritical CO₂-H₂O environment even if the water content reaches a saturated solubility of 0.4114%, and the corrosion rate is 0.0013 mm/a. However, when O₂, H₂S, SO₂and NO₂ coexist in supercritical CO₂-H₂O environment, the corrosion rate of X65 steel increases from 0.0181 mm/a to 0.2901 mm/a as the water content varies from 0.002% to 0.4114%. The impurities and their interactions significantly promote the formation of corrosive aqueous phase, therefore exacerbating the corrosion of X65 steel. The corrosion process of X65 steel in the environment with low water content is controlled by the products of impurity reactions, whereas the impurities and the products of impurity reactions jointly dominate the corrosion process of the steel in the environment with high water content.

Key words： X65 pipeline steel supercritical CO₂ water content impurity corrosion

收稿日期: 2023-07-18 32134.14.1005.4537.2023.227

ZTFLH:

TG178

基金资助:中海油“十四五”重大科研项目(KJGG-2022-12-CCUS-0103)

通讯作者: 孙建波，E-mail：sunjianbo@upc.edu.cn，研究方向为金属腐蚀与防护

Corresponding author: Sun Jianbo, E-mail: sunjianbo@upc.edu.cn

作者简介: 胡丽华，女，1980年生，博士，高级工程师

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https://www.jcscp.org/CN/10.11902/1005.4537.2023.227 或 https://www.jcscp.org/CN/Y2024/V44/I3/576

图1 腐蚀模拟实验装置示意图

表1 腐蚀模拟实验条件 (volume fraction / %)

图2 X65钢的腐蚀速率随水含量的变化规律

图3 在不同含水量的超临界CO2-H2O环境中腐蚀72 h后X65钢的宏观和SEM表面形貌

图4 在不同含水量的超临界CO2-H2O-杂质环境中腐蚀72 h后X65钢的宏观和SEM表面形貌

表2 图4中A~F标记区域腐蚀产物EDS半定量分析结果

图5 在不同含水量的超临界CO2-H2O-杂质环境中腐蚀72 h后X65钢的截面背散射电子像及元素分布

图6 在不同含水量的超临界CO2-H2O-杂质环境中腐蚀72 h后X65钢表面腐蚀膜的XRD图谱

图7 在不同含水量的超临界CO2-H2O-杂质环境中腐蚀72 h后X65钢腐蚀膜中不同元素的高分辨XPS图谱(参照C 1s峰结合能284.8 eV对图谱进行荷电校正)

Element	0.2% H₂O		0.1% H₂O		0.05% H₂O
Element	Binding energy eV	Fitted species	Binding energy eV	Fitted species	Binding energy eV	Fitted species
Fe 2p	710.8	FeSO₄^[20]	710.8	FeSO₄^[20]	711.3	FeSO₄^[20]
	712.2	FeSO₄^[21]	712.2	FeSO₄^[21]	713.6	FeSO₄^[22]
	724.5	FeOOH^[23]	724.5	FeOOH^[23]	725.3	FeOOH^[23]
O 1s	530.1	FeOOH^[24]	529.7	FeOOH^[25]	530.2	FeOOH^[23]
	531.5	FeOOH^[20]	531.7	FeOOH^[25]	531.8	FeOOH^[26]
	532.2	FeSO₄^[21]	533.7	SO $4 2 -$ ^[27]	532.3	FeSO₄^[28]
S 2p	163.7	S^[29]	164.0	S^[30]	-	-
	167.1	SO $3 2 -$ ^[21]	168.7	FeSO₄^[28]	168.7	FeSO₄^[28]
	168.6	FeSO₄^[21]	-	-	-	-

表3 X65钢腐蚀膜XPS图谱中Fe 2p，O 1s和 S 2p的结合能和化合物分析结果

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