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中国腐蚀与防护学报  2026, Vol. 46 Issue (2): 523-532     CSTR: 32134.14.1005.4537.2025.147      DOI: 10.11902/1005.4537.2025.147
  研究报告 本期目录 | 过刊浏览 |
超级13Cr不锈钢在饱和CO2 油田采出液中的缝隙腐蚀行为
陈旭1(), 刘宇航1, 郭建1, 王岐山1, 刘畅2, 刘彬1
1.辽宁石油化工大学石油与天然气工程学院 抚顺 113001
2.中国石油天然气股份有限公司大庆炼化分公司 大庆 163411
Crevice Corrosion Behavior of Super 13Cr Stainless Steel in Saturated CO2 Oilfield Produced Fluids
CHEN Xu1(), LIU Yuhang1, GUO Jian1, WANG Qishan1, LIU Chang2, LIU Bin1
1.College of Petroleum Engineering, Liaoning Petrochemical University, Fushun 113001, China
2.Daqing Refining & Chemical Company, China National Petroleum Corporation, Daqing 163411, China
引用本文:

陈旭, 刘宇航, 郭建, 王岐山, 刘畅, 刘彬. 超级13Cr不锈钢在饱和CO2 油田采出液中的缝隙腐蚀行为[J]. 中国腐蚀与防护学报, 2026, 46(2): 523-532.
Xu CHEN, Yuhang LIU, Jian GUO, Qishan WANG, Chang LIU, Bin LIU. Crevice Corrosion Behavior of Super 13Cr Stainless Steel in Saturated CO2 Oilfield Produced Fluids[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(2): 523-532.

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摘要: 

采用浸泡实验和电化学实验研究了不同缝隙开口宽度下超级13Cr不锈钢在饱和CO2油气田采出液中的缝隙腐蚀行为。结果表明,在温度为60 ℃、CO2压力为1.5 MPa条件下,超级13Cr不锈钢缝隙腐蚀行为主要由CO2水解产物的阴极过程主导。随着缝隙开口宽度的增加,超级13Cr缝隙腐蚀速率增加,钝化膜中Cr2O3逐渐向Cr(OH)3转变。当缝隙宽度为0.125 mm时,缝隙内外物质交换困难,缝内阴极还原物不能得到补充,阴极反应受到抑制,缝内金属仍保持钝化状态,不发生腐蚀;当缝隙宽度为0.25 mm时,缝内外物质交换变得容易,缝内钝化膜在CO2水解产物作用下发生阳极溶解,诱发缝隙内出现点蚀坑,缝内腐蚀速率增大;当缝隙宽度为0.5 mm时,缝内Cl-达到临界浓度,诱发夹杂物溶解导致点蚀。不同缝隙宽度下腐蚀产物均堆积在缝口,但腐蚀产物对物质交换阻碍作用较小。缝口外H+和Cl-浓集,导致缝口外金属发生点蚀。

关键词 超级13Cr不锈钢油田采出液缝隙腐蚀缝隙宽度饱和CO2阴极反应    
Abstract

The crevice corrosion behavior of super 13Cr stainless steel in saturated CO2 oilfield produced fluids in conditions of varying crevice opening widths was investigated using immersion test and electrochemical techniques. The results indicated that under CO2 pressure of 1.5 MPa at 60 ℃, crevice corrosion behavior of super 13Cr was primarily governed by the cathodic process related with CO2 hydrolysis products. With the increase in the width of the crevice opening, the crevice corrosion rate of super 13Cr increases, while the Cr2O3 within the passivation film gradually transformed into Cr(OH)3. When the crevice width was 0.125 mm, substances exchange between the inside and outside of the crevice was restricted. The depletion of cathodic reducing agents within the crevice inhibited the cathodic reaction, allowing the metal to remain in a passivated state with no occurrence of significant corrosion. At a crevice width of 0.25 mm, material exchange between the inside and outside of the crevice was enhanced. Due to the influence of CO2 hydrolysis products, the passive film within the crevice underwent anodic dissolution, leading to the formation of pitting and an increase in the crevice corrosion rate. When the crevice width was 0.5 mm, a critical concentration of Cl- was reached within the crevice, inducing the dissolution of inclusions and subsequent pitting corrosion. Despite these changes, in conditions of pitting corrosion and within a range of the entire tested opening crevice widths, super 13Cr all exhibited passivation performance, forming a surface film composed mainly of Cr2O3 and Cr(OH)2. Regardless of the crevice width, corrosion products tended to accumulate at the crevice openings; however, their impact on the material exchange remained relatively minor. The elevated concentrations of H+ and Cl- near the crevice opening promoted pitting corrosion of the metal outside the crevice.

Key wordssuper 13Cr stainless steel    oilfield produced fluid    crevice corrosion    crevice width    saturated CO2    cathode reaction
收稿日期: 2025-05-14      32134.14.1005.4537.2025.147
ZTFLH:  TG147  
基金资助:辽宁省教育厅基本业务费项目(LJ212410148059)
通讯作者: 陈 旭,E-mail:chenxu@lnpu.edu.cn,研究方向为金属材料腐蚀与防护
作者简介: 陈 旭,女,1974年生,博士,教授
图1  浸泡实验缝隙试样装配图
图2  电化学实验缝隙试样装配图
图3  不同缝隙开口宽度超级13Cr不锈钢浸泡240 h后宏观腐蚀形貌
图4  不同缝隙宽度超级13Cr不锈钢浸泡240 h后腐蚀产物SEM及EDS结果
图5  不同缝隙宽度超级13Cr不锈钢去除腐蚀产物后缝内和缝外SEM形貌
图6  缝隙宽度0.5 mm时缝隙内夹杂物EDS结果
图7  不同缝隙宽度超级13Cr不锈钢在浸泡240 h后XPS全谱
图8  不同缝隙宽度超级13Cr不锈钢浸泡240 h后Cr 2p和O 1s XPS结果
Crevice width/ mmCorrosion productsBinding energy / eVPeak area of CPS / eV
0.125Cr2O3576.53220.44
Cr(OH)3577.79254.09
0.25Cr2O3576.62424.52
Cr(OH)3577.67286.35
0.5Cr2O3576.94493.52
Cr(OH)3577.30407.82
表1  不同缝隙宽度下腐蚀产物中Cr元素组成对应结合能及峰面积
图9  缝隙内外超级13Cr不锈钢的开路电位
图10  不同缝隙宽度超级13Cr不锈钢浸泡240 h后极化曲线结果
Crevice width / mmEcorr / VIpass / μA·cm-2Passivation range / mVEtp / V
0.125-0.6053.98197-0.283
0.25-0.56221.50170-0.243
0.5-0.501147.9196-0.137
表2  不同缝隙宽度下超级13Cr不锈钢极化曲线拟合结果
图11  超级13Cr不锈钢在不同缝隙宽度下EIS结果
图12  不同缝隙宽度超级13Cr不锈钢浸泡240 h后EIS结果
图13  EIS结果拟合所采用的等效电路
Crevice width / mmTime / hRs / Ω·cm2Qf / F·cm-2Rf / Ω·cm2Qdl / F·cm-2Rct / Ω·cm2W / 10-3 Ω·cm-2
0.12524456.01.1 × 10-712907.4 × 10-54.6 × 1047.5
120557.01.3 × 10-612804.9 × 10-55.5 × 1047.1
240690.07.1 × 10-613702.3 × 10-57.1 × 1048.3
0.2524107.31.6 × 10-51331.2 × 10-43.8 × 1031.2
120105.81.4 × 10-41551.5 × 10-54.2 × 1031.4
240109.31.2 × 10-41921.2 × 10-45.6 × 1032.1
0.52432.51.0 × 10-41602.2 × 10-44.5 × 1032.3
12024.91.3 × 10-42211.5 × 10-46.6 × 1031.8
24027.31.4 × 10-41251.5 × 10-43.3 × 1031.9
表3  不同缝隙宽度超级13Cr不锈钢EIS拟合结果
图14  不同缝隙宽度超级13Cr不锈钢不同浸泡时间下Rct值
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