D01:10.13374.isml00103x.2009.06.010 第31卷第5期 北京科技大学学报 Vol.31 No.5 2009年5月 Journal of University of Science and Technology Beijing May 2009 高含H2S/C02介质中X60钢腐蚀产物膜分析 张雷D 睿明2》杨建炜路民旭》 1)北京科技大学材料科学与工程学院北京1000832)中国石油天然气管道工程有限公司，廊坊065000 摘要利用高温高压H2S反应釜进行腐蚀模拟实验，研究X60钢在高压HS/CO2共存条件下的腐蚀规律，并利用扫描电子 显微镜和X射线衍射等方法观察用分析了腐蚀产物膜的形貌和组成.在H2S/C02分压比为1.74HS分压Q15~2.0MPa 条件下，腐蚀产物以硫铁化合物为主，未见碳酸亚铁X60钢腐蚀过程由HS控制.HS分压较低时腐蚀产物以四方FS1-x为 主.H2S分压20MP时则出现六方FS、六方Fe1-S和立方FS2.疏松的富S腐蚀产物及腐蚀产物膜局部剥落促使高HS 分压时X60钢出现明显局部腐蚀并使全面腐蚀速率随HS分压升高先升后降. 关键词X60钢：气体腐蚀：腐蚀产物膜：局部腐蚀 分类号TG172.3+3 Analysis of corrosion scales on X60 steel under high H2S/CO content environ- ments ZHANG Lei.DING Rui-ming2.YANG Jian-wei.LU Minxu 1)School of Materials Science and Engineering.University of Science and Techndlogy Beijing.Beijing 100083.China 2)China Petroleum Pipeine Engineering Comporation.Langfarg 065000.China ABSTRACT Corrosion of X60 steel under higlpressure H2S CO2 coexist environment was investigated using a high-temperature and highrpressure H2S autoclave.The structure and constitution of corrosion scales were studied through scanning electron microscopy (SEM)and X-ray diffraction (XRD).Corrosion experiments were carried out under situations with the same H2S/CO2 partial pres- sure ratio (1.74)and different H2S partial pressures from 0 15 MPa to 2.0 MPa.The results show that the corrosion scales mainly consist of ferrous sulfide.The absence of ferrous carbonate in the corrosion scales suggests that the corrosion process was controlled by H2S.Under low H2S partial pressure conditions tetragonal FeS-xis the predominant corrosion product.When the H2S partial pres- sure was increased to 2.0 MPa hex agonal FeS,hexagonal Fe-S and cubic FeS2 could also be observed in the corrosion scales.Lo- calized corrosion observed on X60 steel under a higher H2S partial pressure condition can be attributed to the loose scale with S-rich corrosion products and the local breaking of corrosion scales which also induced the decreasing of general corrosion rate at a higher H2S partial pressure level. KEY WORDS X60 steek gas corrosion;corrosion scale;localized corrosion 随着我国高含硫油气田的开发及国外含硫天然 HS/CO2共存条件下的腐蚀控制模式习，H2S和 气的引进，高含H2S、HS/C02共存等苛刻条件下油 C02含量的改变进一步影响腐蚀产物的组成和结 气生产和输送管材的腐蚀已成为影响油气安全生产 构.H2S/C02共存时形成的腐蚀产物主要是不同结 和运输的突出问题，也是近些年国际腐蚀研究的热 构的硫铁化合物(FexSy)、碳酸亚铁(FeCO3)和铁的 点问题.HS、C02溶于水后均对钢铁材料具有强烈 氧化物FexOr):随着环境条件的变化腐蚀产 的腐蚀性，当两者共存时，H2S/C02的分压比决定 物膜的形态、结构和稳定性都会发生变化，并进一步 收稿日期：200804-23 基金项目：国家自然科学基金资助项目(No.50701007) 作者简介：张雷(1978一)，男.讲师，博士，E-maik zhanglei@m威.ust h edu.cn高含 H2S/CO2 介质中 X60 钢腐蚀产物膜分析 张 雷 1) 丁睿明 1, 2) 杨建炜 1) 路民旭 1) 1)北京科技大学材料科学与工程学院, 北京 100083 2)中国石油天然气管道工程有限公司, 廊坊 065000 摘 要 利用高温高压 H2 S 反应釜进行腐蚀模拟实验, 研究 X60 钢在高压H2S/CO2 共存条件下的腐蚀规律, 并利用扫描电子 显微镜和 X 射线衍射等方法观察用分析了腐蚀产物膜的形貌和组成.在 H2S/CO2 分压比为 1.74、H2S 分压 0.15 ～ 2.0 MPa 条件下, 腐蚀产物以硫铁化合物为主 , 未见碳酸亚铁, X60 钢腐蚀过程由 H2S 控制.H2S 分压较低时腐蚀产物以四方 FeS1 -x为 主, H2 S 分压 2.0 MPa 时则出现六方 FeS 、六方 Fe1 -xS 和立方 FeS2 .疏松的富 S 腐蚀产物及腐蚀产物膜局部剥落促使高 H2S 分压时 X60 钢出现明显局部腐蚀, 并使全面腐蚀速率随 H2S 分压升高先升后降. 关键词 X60 钢;气体腐蚀;腐蚀产物膜;局部腐蚀 分类号 TG172.3 +3 Analysis of corrosion scales on X60 steel under high H2S/CO2 content environ￾ments ZHANG Lei 1), DING Rui-ming 1 , 2), Y ANG Jian-wei 1), LU Min-x u 1) 1)School of Mat erials Science and Engineering , University of S cience and Technology Beijing , Beijing 100083 , China 2)China Petroleum Pipeline Engineering Corporation , Langfang 065000 , China ABSTRACT Corrosion of X60 steel under hig h-pressure H2 S/ CO2 coex ist environment was investig ated using a high-temperature and hig h-pressure H2 S autoclave.The structure and constitution of corrosion scales were studied through scanning electron microscopy (SEM)and X-ray diffraction (XRD).Co rrosion experiments were carried out under situations with the same H2S/CO2 partial pres￾sure ratio (1.74)and different H2 S partial pressures from 0.15 MPa to 2.0 MPa.The results show that the corro sion scales mainly consist of ferrous sulfide.The absence of ferrous carbonate in the corrosion scales sugg ests that the corrosion process w as controlled by H2S .Under low H2 S partial pressure conditio ns, tetragonal FeS1 -x is the predominant corrosion product .When the H2S partial pres￾sure was increased to 2.0 MPa , hex ag onal FeS , hexagonal Fe1 -xS and cubic FeS2 could also be observed in the co rrosion scales.Lo￾calized corrosion observed on X60 steel under a higher H2 S partial pressure condition can be attributed to the loose scale with S-rich corrosion products and the local breaking of corrosion scales, w hich also induced the decreasing of general corrosio n rate a t a higher H2S partial pressure level . KEY WORDS X60 steel;gas co rrosion ;corrosion scale;localized corrosion 收稿日期:2008-04-23 基金项目:国家自然科学基金资助项目(No .50701007) 作者简介:张 雷(1978—), 男, 讲师, 博士, E-mail:zhanglei@mat er .ustb.edu.cn 随着我国高含硫油气田的开发及国外含硫天然 气的引进 ,高含 H2S 、H2S/CO2 共存等苛刻条件下油 气生产和输送管材的腐蚀已成为影响油气安全生产 和运输的突出问题 ,也是近些年国际腐蚀研究的热 点问题.H2S 、CO2 溶于水后均对钢铁材料具有强烈 的腐蚀性 , 当两者共存时, H2S/CO2 的分压比决定 H2S/CO2 共存条件下的腐蚀控制模式 [ 1-2] , H2S 和 CO2 含量的改变进一步影响腐蚀产物的组成和结 构 .H2S/CO2 共存时形成的腐蚀产物主要是不同结 构的硫铁化合物(FeXS Y)、碳酸亚铁(FeCO3)和铁的 氧化物(FeXOY )[ 3-7] ;随着环境条件的变化, 腐蚀产 物膜的形态 、结构和稳定性都会发生变化 ,并进一步 第 31 卷 第 5 期 2009 年 5 月 北 京 科 技 大 学 学 报 Journal of University of Science and Technology Beijing Vol .31 No.5 May 2009 DOI :10.13374/j .issn1001 -053x.2009.05.010