湿气环境中抗硫钢的元素硫腐蚀特征及腐蚀机理

doi:10.11902/1005.4537.2021.162

中国腐蚀与防护学报

2022, Vol. 42

Issue (3): 369-377 DOI: 10.11902/1005.4537.2021.162

中国腐蚀与防护学会杰出青年学术成就奖论文专栏

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湿气环境中抗硫钢的元素硫腐蚀特征及腐蚀机理

刘毅超¹, 钟显康¹^,²(

), 扈俊颖¹

^1.西南石油大学石油与天然气工程学院成都 610500
^2.油气藏地质及开发工程国家重点实验室 (西南石油大学) 成都 610500

Characteristics and Mechanisms of Elemental Sulfur Induced Corrosion of Sulfur-resistant Steels in Wet Flow CO₂ Environment

LIU Yichao¹, ZHONG Xiankang¹^,²(

), HU Junying¹

^1.School of Oil and Natural Gas Engineering, Southwest Petroleum University, Chengdu 610500, China
^2.State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu 610500, China

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摘要:

探究了CO₂湿气环境中P110SS抗硫钢在不同温湿度下的S腐蚀特征及腐蚀机理。采用X射线光电子能谱 (XPS) 和扫描电子显微镜 (SEM)，对P110SS钢表面腐蚀产物膜的化学组成、微观形貌及厚度及去除腐蚀产物后基体的微观形貌进行了表征。结果表明：在60 ℃、相对湿度为30%的条件下，S不会参与腐蚀反应，但腐蚀环境中的Cl^-和CO₂会导致抗硫钢发生局部腐蚀；当相对湿度升高至60%和90%时，S参与了腐蚀的阴极反应，生成FeS，并导致抗硫钢发生全面腐蚀。在80 ℃、相对湿度为30%的条件下，S也参与腐蚀的阴极反应，并导致抗硫钢发生了局部腐蚀；当相对湿度为60%和90%时，S会发生水解反应，产生H₂S和H₂SO₄，使抗硫钢发生严重的全面腐蚀。另外，腐蚀产物膜的厚度随湿度的升高而增加，致密度随反应温度的升高而降低。研究结果能为抗硫钢的S腐蚀控制提供参考。

关键词 ：湿气环境, S腐蚀, P110SS, 腐蚀特征, 腐蚀机理

Abstract：

The characteristics and mechanisms of elemental sulfur induced corrosion of P110SS sulfur-resistant steel in wet flow carbon dioxide atmosphere of various flux and relative humidity at different temperatures were investigated by means of X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), in terms of the composition and morphology of the corrosion product and the substrate steel. The results show that the elemental sulfur does not corrode P110SS at 60 ℃ in the wet flow CO₂ with 30% relative humidity, however when the relative humidity reaches to 60% or higher, the elemental sulfur may participate in the cathodic reaction to generate S^2-, which in turn combines with Fe²⁺ to produce FeS. As the temperature reaches to 80 ℃, the elemental sulfur becomes more active and may react with the steel to form FeS even in the flow CO₂ with 30% relative humidity. When the relative humidity reaches to 60% or higher at 80 ℃, the elemental sulfur starts to hydrolyze, generating H₂SO₄ and H₂S, which aggravates the corrosion of the steel. Furthermore, when the CO₂ flux with high humidity at high temperature, FeS will also catalyze the hydrolysis of the elemental sulfur to form more SO₄^2- and S^2-. Finally, the thickness of the corrosion product increases with the increasing humidity and the density of the corrosion product decreases with the increasing temperature. Therefore, the findings of this study can provide a reference for the prevention and control of the elemental sulfur corrosion of sulfur-resistant steels.

Key words： humid environment elemental sulfur corrosion P110SS sulfur-resistant steel corrosion characteristics corrosion mechanisms

收稿日期: 2021-07-13

ZTFLH:

TG172

基金资助:国家自然科学基金(52171080);西南石油大学青年科技创新团队项目(2018CXTD01)

通讯作者: 钟显康 E-mail: zhongxk@yeah.net

Corresponding author: ZHONG Xiankang E-mail: zhongxk@yeah.net

作者简介: 刘毅超，男，1996年生，硕士生

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引用本文:

刘毅超, 钟显康, 扈俊颖. 湿气环境中抗硫钢的元素硫腐蚀特征及腐蚀机理[J]. 中国腐蚀与防护学报, 2022, 42(3): 369-377.
Yichao LIU, Xiankang ZHONG, Junying HU. Characteristics and Mechanisms of Elemental Sulfur Induced Corrosion of Sulfur-resistant Steels in Wet Flow CO₂ Environment. Journal of Chinese Society for Corrosion and protection, 2022, 42(3): 369-377.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.162 或 https://www.jcscp.org/CN/Y2022/V42/I3/369

图1 P110SS钢的金相组织

图2 实验装置示意图

表1 反应瓶内的相对湿度

图3 60 ℃、不同相对湿度下S (2p3/2)、Fe (2p3/2) 和Mo (3d3/2) 的XPS高分辨谱

表2 不同温湿度下各物质峰面积比

图4 80 ℃、不同相对湿度下S (2p3/2)、Fe (2p3/2) 和Mo (3d3/2) 的XPS高分辨谱

图5 不同温湿度下覆盖S的P110SS钢表面腐蚀产物形貌

图6 不同温湿度下覆盖S的P110SS钢腐蚀截面SEM图

图7 不同温湿度下覆盖S的P110SS钢表面去膜后形貌

图8 30%RH/60 ℃条件下覆盖物不含S时的P110SS钢表面去膜后形貌

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