H<sub>2</sub>S分压对13Cr不锈钢在CO<sub>2</sub>注气井环空环境中应力腐蚀行为的影响

doi:10.11902/1005.4537.2013.038

中国腐蚀与防护学报

2014, Vol. 34

Issue (1): 46-52 DOI: 10.11902/1005.4537.2013.038

本期目录 | 过刊浏览

H₂S分压对13Cr不锈钢在CO₂注气井环空环境中应力腐蚀行为的影响

王峰^1,²(

), 韦春艳³, 黄天杰^1,⁴, 崔中雨⁵, 李晓刚⁵

1. 国家能源CO₂驱油与埋存研发 (实验) 中心松原 138000
2. 东北石油大学提高油气采收率教育部重点实验室大庆 163318
3. 吉林油田公司扶余采油厂松原 138003
4. 吉林油田公司采油工艺研究院松原 138003
5. 北京科技大学腐蚀与防护中心北京 100083

Effect of H₂S Partial Pressure on Stress Corrosion Cracking Behavior of 13Cr Stainless Steel in Annulus Environment Around CO₂ Injection Well

WANG Feng^1,²(

), WEI Chunyan³, HUANG Tianjie^1,⁴, CUI Zhongyu⁵, LI Xiaogang⁵

1. National Energy CCS-EOR R&D (Experimental) Center, Songyuan 138000, China
2. Key Laboratory for Enhancing Oil Recovery of the Ministry of Education, Northeast Petroleum University, Daqing 163318, China
3. Fuyu Oil Production Plant, Jilin Oil Field Company, Songyuan 138003, China
4. Oil Production Technology Institute, Jilin Oil Field Company, Songyuan 138003, China
5. Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China

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摘要:

利用高压下的电化学实验及U型弯浸泡实验结合微观分析手段,研究了13Cr不锈钢在不同H₂S分压下CO₂注气井环空环境模拟液中的电化学特征及应力腐蚀规律。结果表明：油套管钢的刺漏现象以及环境中硫酸盐还原菌的存在使得环空环境成为复杂的高压H₂S-CO₂-Cl^-环境,13Cr不锈钢在该种环境下具有明显的应力腐蚀敏感性。随着H₂S分压的升高,13Cr不锈钢击破电位下降,应力腐蚀敏感性增强,这主要因为H₂S分压的增大对不锈钢表面膜 (钝化膜及腐蚀产物膜) 的破坏作用加强。当H₂S分压达到0.20 MPa时,13Cr不锈钢发生明显的应力腐蚀,断口表现为由沿晶应力腐蚀裂纹 (IGSCC) 和穿晶应力腐蚀裂纹 (TGSCC) 组成的混合断口,应力腐蚀受阳极溶解和氢致开裂共同控制。

关键词 ： 13Cr不锈钢, H₂S/CO₂, 应力腐蚀, H₂S分压

Abstract：

Electrochemical characteristics and stress corrosion cracking (SCC) behavior of 13Cr stainless steel were investigated by electrochemical measurements, U-bent specimen immersion test and surface analysis technique in an artificial solution with an autoclave, which aimed to simulate the annulus environment around CO₂ injection well. The results showed that annulus solution around injection well was a complicated H₂S-CO₂-Cl^- environment which generated the SCC of 13Cr stainless steel. The pitting breakthrough potential and SCC resistance of 13Cr stainless steel decreased obviously with increasing H₂S partial pressure, which is associated with the deterioration of surface film (passive film and corrosion products scales) on the steel. When the H₂S partial pressure exceeded 0.20 MPa (including 0.20), SCC occurred on 13Cr steel. Typical transgranular and intergranular fracture morphologies were observed, which indicated that the SCC process was mixed-controlled by both anodic dissolution and hydrogen-induced cracking.

Key words： 13Cr stainless steel H₂S/CO₂ stress corrosion cracking H₂S partial pressure

收稿日期: 2013-04-24

ZTFLH:

TG172

基金资助:国家自然科学基金重点项目 (51131001);松辽盆地含CO₂气藏开发及利用示范工程项目 (2012ZX05054)资助

作者简介: null

王峰,男,1973年生,高级工程师,研究方向为采气工艺、CO₂驱油技术

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引用本文:

王峰, 韦春艳, 黄天杰, 崔中雨, 李晓刚. H₂S分压对13Cr不锈钢在CO₂注气井环空环境中应力腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2014, 34(1): 46-52.
Feng WANG, Chunyan WEI, Tianjie HUANG, Zhongyu CUI, Xiaogang LI. Effect of H₂S Partial Pressure on Stress Corrosion Cracking Behavior of 13Cr Stainless Steel in Annulus Environment Around CO₂ Injection Well. Journal of Chinese Society for Corrosion and protection, 2014, 34(1): 46-52.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2013.038 或 https://www.jcscp.org/CN/Y2014/V34/I1/46

图1 13Cr不锈钢的金相组织

Condition	Temperarure / ℃	pH	Corrosion inhibitor	CO₂ partial pressure / MPa	Total pressure / MPa	H₂S partial pressure / MPa	$P C O 2 / P H 2 S$
1	25	4.0	1×10^-³	4.0	9.0	0	---
2	25	4.0	1×10^-³	4.0	9.0	0.05	80
3	25	4.0	1×10^-³	4.0	9.0	0.10	40
4	25	4.0	1×10^-³	4.0	9.0	0.20	20
5	25	4.0	1×10^-³	4.0	9.0	0.30	13.3

表1 13Cr不锈钢电化学测试条件

图2 13Cr不锈钢在不同H2S分压条件下的极化曲线

图3 13Cr不锈钢在不同H2S分压下的EIS谱

表2 13Cr不锈钢在不同H2S分压下的EIS谱拟合结果

图4 极化电阻 (Rp)、维钝电流 (ipass) 及膜电阻 (Rf) 随H2S分压的变化曲线

图5 13Cr不锈钢U型弯试样浸泡后的宏观形貌

图6 13Cr不锈钢U型弯断裂时间随H2S分压的变化曲线

图7 13Cr不锈钢U型弯浸泡后的断口形貌

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