低Cr钢在CO_2/H_2S环境中的腐蚀行为研究
|
摘要
目的研究低Cr钢(3%～9%)在60℃的CO_2/H_2S环境中的腐蚀行为。方法将三种低Cr钢(3Cr-H、5Cr-H、9Cr-H)加热到900℃之后,保温40min,进行水冷。对热处理之后的钢试样(依次编号3Cr-H、5Cr-H、9Cr-H)进行高温高压CO_2/H_2S腐蚀模拟实验,通过扫描电子显微镜(SEM)、能谱分析仪(EDS)和X射线衍射仪(XRD)对腐蚀产物膜的微观形貌和成分以及物相组成进行分析。结果 3Cr、5Cr、9Cr钢的腐蚀速率分别为0.0443、0.0372、0.0060 mm/a,且腐蚀速率随着Cr含量的增加而降低。3Cr-H、5Cr-H、9Cr-H钢的腐蚀速率分别为0.1527、0.0445、0.0070mm/a,其腐蚀速率也是随着Cr含量的增加而降低。其中,3Cr-H钢的腐蚀速率是3Cr钢的3.4倍,耐蚀性能变化明显。5Cr-H钢的腐蚀速率是5Cr钢的1.19倍。9Cr-H钢的腐蚀速率与9Cr钢相比,几乎没有差别。六种材料的腐蚀产物均为FeS化合物,并没有发现典型的FeCO_3晶体(CO_2腐蚀产物)。3Cr、5Cr、3Cr-H、5Cr-H钢的腐蚀产物均为双层膜结构,9Cr、9Cr-H钢的腐蚀产物为单层膜结构。结论热处理未影响腐蚀速率随Cr含量的变化趋势,基体中Cr含量越高,腐蚀产物膜中的Cr富集量越大,从而有助于降低其腐蚀速率。热处理对3Cr钢的显微组织及其腐蚀行为影响最为显著,不仅加剧了其均匀腐蚀,而且促进了点蚀的发生,这是因为热处理后,显微组织中析出第二相含Cr的碳化物,使部分区域出现了贫Cr的现象。
The work aims to study the corrosion behavior of low Cr steels(3%～9%) in CO_2/H_2S environment at 60 ℃.Three kinds of low Cr steels were heated to 900 ℃ and then water-cooled for 40 minutes. CO2/H2 S corrosion tests were carried out to 3 Cr-H, 5 Cr-H and 9 Cr-H steel samples in an autoclave. Morphologies, compositions and phase of corrosion products were analyzed by scanning electron microscopy(SEM), energy dispersive spectrometer(EDS), and X-ray diffraction(XRD). The corrosion rates of 3 Cr, 5 Cr and 9 Cr steels were 0.0443, 0.0372 and 0.006 mm/a, respectively. The corrosion rates decreased with the increase of Cr content. The corrosion rates of 3 Cr-H, 5 Cr-H and 9 Cr-H steels were 0.1527, 0.0445 and 0.007 mm/a, respectively. The corrosion rates also decreased with the increase of Cr content. The corrosion rate of 3 Cr-H steel was 3.4 times that of3 Cr steel, and the corrosion resistance changed obviously. The corrosion rate of 5 Cr-H steel was 1.19 times that of 5 Cr steel. The corrosion rate of 9 Cr-H steel was almost the same as that of 9 Cr steel. The corrosion products of the six materials were all FeS compounds, and no typical FeCO_3 crystals(CO_2 corrosion product) were found. The corrosion products of 3 Cr, 5 Cr, 3 Cr-H and5 Cr-H steels were of double-layer structure, while those of 9 Cr and 9 Cr-H steels were of single-layer structure. Heat treatment does not affect the trend between the content of Cr and corrosion rate. The higher the content of Cr in the matrix is, the greater the concentration of Cr in the corrosion product film, which helps to reduce the corrosion rate; Heat treatment has the most significant effect on the microstructure and corrosion behavior of 3 Cr steel, which not only aggravates the uniform corrosion, but also promotes pitting corrosion. This is due to the precipitation of second phase carbides containing Cr in the microstructure after heat treatment, thus resulting in the phenomenon of poor Cr in some areas.
The work aims to study the corrosion behavior of low Cr steels(3%～9%) in CO_2/H_2S environment at 60 ℃.Three kinds of low Cr steels were heated to 900 ℃ and then water-cooled for 40 minutes. CO2/H2 S corrosion tests were carried out to 3 Cr-H, 5 Cr-H and 9 Cr-H steel samples in an autoclave. Morphologies, compositions and phase of corrosion products were analyzed by scanning electron microscopy(SEM), energy dispersive spectrometer(EDS), and X-ray diffraction(XRD). The corrosion rates of 3 Cr, 5 Cr and 9 Cr steels were 0.0443, 0.0372 and 0.006 mm/a, respectively. The corrosion rates decreased with the increase of Cr content. The corrosion rates of 3 Cr-H, 5 Cr-H and 9 Cr-H steels were 0.1527, 0.0445 and 0.007 mm/a, respectively. The corrosion rates also decreased with the increase of Cr content. The corrosion rate of 3 Cr-H steel was 3.4 times that of3 Cr steel, and the corrosion resistance changed obviously. The corrosion rate of 5 Cr-H steel was 1.19 times that of 5 Cr steel. The corrosion rate of 9 Cr-H steel was almost the same as that of 9 Cr steel. The corrosion products of the six materials were all FeS compounds, and no typical FeCO_3 crystals(CO_2 corrosion product) were found. The corrosion products of 3 Cr, 5 Cr, 3 Cr-H and5 Cr-H steels were of double-layer structure, while those of 9 Cr and 9 Cr-H steels were of single-layer structure. Heat treatment does not affect the trend between the content of Cr and corrosion rate. The higher the content of Cr in the matrix is, the greater the concentration of Cr in the corrosion product film, which helps to reduce the corrosion rate; Heat treatment has the most significant effect on the microstructure and corrosion behavior of 3 Cr steel, which not only aggravates the uniform corrosion, but also promotes pitting corrosion. This is due to the precipitation of second phase carbides containing Cr in the microstructure after heat treatment, thus resulting in the phenomenon of poor Cr in some areas.
引文
[1]张忠铧,郭金宝.CO2对油气管材的腐蚀规律及国内外研究进展[J].宝钢技术,2000(4):54-58.ZHANG Zhong-hua,GUO Jin-bao.Law of CO2 corrosion of oil country tubular goods and the study of its progress athome and abroad[J].Baosteel technology,2000(4):54-58.
[2]王献昉,董振江,梁拥军,等.经济型低Cr抗CO2腐蚀合金石油管材钢开发现状[J].腐蚀科学与防护技术,2006,18(6):436-439.WANG Xian-fang,DONG Zhen-jiang,LIANG Yong-jun,et al.Development of economic steels with low Cr content for anti-corrosion oil tube[J].Corrosion science and protection technology,2006,18(6):436-439.
[3]KERMANI M B,GONZALES J C,TURCONI G L,et al.Development of superior for corrosion resistance 3%Cr steels for downhole applications corrosion[C]//57th NACE Annual Conf.Houston:NACE,2001.
[4]KERMANI M B,GONZALES J C,LINNE C,et al.Development of low carbon Cr-Mo steels with exceptional corrosion resistance for oil field applications[C]//56th NACE Annual Conf.Houston:NACE,2001:65.
[5]UEDA M,TAKABE H,The formation behavior of corrosion protective films of low Cr bearing steels in CO2 environments[C]//NACE International Conference.Houston:[s.n.],2001.
[6]于少波,赵国仙,韩勇.模拟塔里木油田环境中低Cr钢的H2S/CO2腐蚀行为[J].腐蚀与防护,2009,30(5):289-292.YU Shao-bo,ZHAO Guo-xian,HAN Yong.H2S/CO2corrosion behavior of low-Cr steel in simulated tarimoilfield environments[J].Corrosion&protection,2009,30(5):289-292.
[7]WU Q,ZHANG Z,DONG X,et al.Corrosion behavior of low-alloy steel containing 1%chromium in CO2,environments[J].Corrosion science,2013,75(7):400-408.
[8]JIANBO S,CHONG S,LIN X Q,et al.Effect of chromium on corrosion behavior of P110 steels in CO2-H2Senvironment with high pressure and high temperature[J].Materials,2016,9(3):200.
[9]LIU Z,GAO X,DU L,et al.Corrosion behavior of low-alloy steel with martensite/ferrite microstructure at vapor-saturated CO2,and CO2-saturated brine conditions[J].Applied surface science,2015,351:610-623.
[10]朱培珂,邓金根,闫伟,等.3Cr钢和13Cr钢在高矿化度CO2环境中的腐蚀行为[J].腐蚀与防护,2014,35(12):1221-1225.ZHU Pei-ke,DENG Jin-gen,YAN Wei,et al.Corrosion behavior of 3Cr and 13Cr in high salinity brine and CO2environment[J].Corrosion&protection,2014,35(12):1221-1225.
[11]MASAKATSU U,HIDEKI T.Corrosion resistance of low Cr bearing steel in sweet and sour environments[C]//57th NACE Annual Conf.Houston:NACE,2002:41.
[12]XIE Y,XU L,GAO C,et al.Corrosion behavior of novel3%Cr pipeline steel in CO2,top-of-line corrosion environment[J].Materials&design,2012,36:54-57.
[13]XU L,WANG B,ZHU J,et al.Effect of Cr content on the corrosion performance of low-Cr alloy steel in a CO2,top-of-line corrosion environment[J].Applied surface science,2016,379:39-46.
[14]孙建波,苏鑫,张勇,等.高温高压H2S/CO2腐蚀产物膜对低铬钢氢渗透行为的影响[J].表面技术,2018,47(6):17-23.SUN Jian-bo,SU Xin,ZHANG yong,et al.Effect of H2S/CO2 corrosion scales on the hydrogen permeation behavior of low chromium steels[J].Surface technology,2018,47(6):17-23.
[15]LIU Z,GAO X,DU L,et al.Comparison of corrosion behaviour of low-alloy pipeline steel exposed to H2S/CO2-saturated brine and vapour-saturated H2S/CO2environments[J].Electrochimica acta,2017,232:528-541.
[16]YU C,GAO X,WANG H.Corrosion characteristics of low alloy steel under H2S/CO2 environment:experimental analysis and theoretical research[J].Materials letters,2017,209:459-462.
[17]CHOI Y S,NESIC S,LING S.Effect of H2S on the CO2corrosion of carbon steel in acidic solutions[J].Electrochimica acta,2010,56(4):1752-1760.
[18]MU G N,LI X H,QU Q,et al.Molybdate and tungstate as crrosion inhibitors for cold rolling steel in hydrochloric acid solution[J].Corrosion science,2006,48(2):445-459.
[19]LóPEZ D A,PéREZ T,SIMISON S N.The influence of microstructure and chemical composition of carbon and low alloy steels in CO2 corrosion.A state-of-the-art appraisal[J].Materials&design,2003,24(8):561-575.
[20]FAN X,XU L,ZHU J Y,et al.Effects of heat treatment on mechanical properties and CO2 corrosion resistance of3Cr Steel[C]//Corrosion 2015.USA:NACE International,2015.
[21]LI W,XU L,QIAO L,et al.Effect of free Cr content on corrosion behavior of 3Cr steels in a CO2 environment[J].Applied surface science,2017,425:32-45.
[22]NACE SP0775-2018,Preparation,installation,analysis,and interpretation of corrosion coupons in oilfield operations[S].
[23]SUN J B,SUN C,LIN X Q,et al.Effect of chromiumon the corrosion behavior of P110 steels in CO2-H2S environment with high pressure and high temperature[J].Materials,2016,9(3):200.
[24]ZHOU C,ZHENG S,CHEN C,et al.The effect of the partial pressure of H2S on the permeation of hydrogen in low carbon pipeline steel[J].Corrosion science,2013,67(1):184-192.
[25]苏鑫.H2S/CO2环境低铬钢腐蚀产物膜形成机理及氢渗透行为研究[D].青岛:中国石油大学(华东),2013.SU Xin.The formation mechanism of corrosion scale and hydrogen permeation behavior of low chromium steel under H2S/CO2 environment[D].Beijing:China University of Petroleum,2013.
[26]秋兴利,薛玉娜,王荣.3Cr钢在3.5%NaCl溶液中的腐蚀行为[J].材料保护,2014,47(3):12-19.QIU Xing-li,XUE Yu-na,WANG Rong.Corrosion behavior of low chromium steel in 3.5%sodium chloride solution[J].Materials protection,2014,47(3):12-19.
[27]吕祥鸿,赵国仙,王宇,等.低铬抗硫套管的H2S/CO2腐蚀行为研究[J].钢铁研究学报,2010,22(7):23-28.LYU Xiang-hong,ZHAO Guo-xian,WANG Yu,et al.Study on H2S/CO2 corrosion behaviors of low-Cr acid resistant casing steel[J].Journal of iron and steel research,2010,22(7):23-28.
[28]MOHAMMADI A H,NADERI M,IRANMANESH M.Fracture toughness evaluation of 3Cr-1Mo steel from vickers indentation and tensile test data[J].Procedia engineering,2011,10:228-235.
[29]LIU Z,GAO X,DU L,et al.Corrosion behavior of low-alloy steel with martensite/ferrite microstructure at vapor-saturated CO2 and CO2-saturated brine conditions[J].Applied surface science,2015,351:610-623.
[2]王献昉,董振江,梁拥军,等.经济型低Cr抗CO2腐蚀合金石油管材钢开发现状[J].腐蚀科学与防护技术,2006,18(6):436-439.WANG Xian-fang,DONG Zhen-jiang,LIANG Yong-jun,et al.Development of economic steels with low Cr content for anti-corrosion oil tube[J].Corrosion science and protection technology,2006,18(6):436-439.
[3]KERMANI M B,GONZALES J C,TURCONI G L,et al.Development of superior for corrosion resistance 3%Cr steels for downhole applications corrosion[C]//57th NACE Annual Conf.Houston:NACE,2001.
[4]KERMANI M B,GONZALES J C,LINNE C,et al.Development of low carbon Cr-Mo steels with exceptional corrosion resistance for oil field applications[C]//56th NACE Annual Conf.Houston:NACE,2001:65.
[5]UEDA M,TAKABE H,The formation behavior of corrosion protective films of low Cr bearing steels in CO2 environments[C]//NACE International Conference.Houston:[s.n.],2001.
[6]于少波,赵国仙,韩勇.模拟塔里木油田环境中低Cr钢的H2S/CO2腐蚀行为[J].腐蚀与防护,2009,30(5):289-292.YU Shao-bo,ZHAO Guo-xian,HAN Yong.H2S/CO2corrosion behavior of low-Cr steel in simulated tarimoilfield environments[J].Corrosion&protection,2009,30(5):289-292.
[7]WU Q,ZHANG Z,DONG X,et al.Corrosion behavior of low-alloy steel containing 1%chromium in CO2,environments[J].Corrosion science,2013,75(7):400-408.
[8]JIANBO S,CHONG S,LIN X Q,et al.Effect of chromium on corrosion behavior of P110 steels in CO2-H2Senvironment with high pressure and high temperature[J].Materials,2016,9(3):200.
[9]LIU Z,GAO X,DU L,et al.Corrosion behavior of low-alloy steel with martensite/ferrite microstructure at vapor-saturated CO2,and CO2-saturated brine conditions[J].Applied surface science,2015,351:610-623.
[10]朱培珂,邓金根,闫伟,等.3Cr钢和13Cr钢在高矿化度CO2环境中的腐蚀行为[J].腐蚀与防护,2014,35(12):1221-1225.ZHU Pei-ke,DENG Jin-gen,YAN Wei,et al.Corrosion behavior of 3Cr and 13Cr in high salinity brine and CO2environment[J].Corrosion&protection,2014,35(12):1221-1225.
[11]MASAKATSU U,HIDEKI T.Corrosion resistance of low Cr bearing steel in sweet and sour environments[C]//57th NACE Annual Conf.Houston:NACE,2002:41.
[12]XIE Y,XU L,GAO C,et al.Corrosion behavior of novel3%Cr pipeline steel in CO2,top-of-line corrosion environment[J].Materials&design,2012,36:54-57.
[13]XU L,WANG B,ZHU J,et al.Effect of Cr content on the corrosion performance of low-Cr alloy steel in a CO2,top-of-line corrosion environment[J].Applied surface science,2016,379:39-46.
[14]孙建波,苏鑫,张勇,等.高温高压H2S/CO2腐蚀产物膜对低铬钢氢渗透行为的影响[J].表面技术,2018,47(6):17-23.SUN Jian-bo,SU Xin,ZHANG yong,et al.Effect of H2S/CO2 corrosion scales on the hydrogen permeation behavior of low chromium steels[J].Surface technology,2018,47(6):17-23.
[15]LIU Z,GAO X,DU L,et al.Comparison of corrosion behaviour of low-alloy pipeline steel exposed to H2S/CO2-saturated brine and vapour-saturated H2S/CO2environments[J].Electrochimica acta,2017,232:528-541.
[16]YU C,GAO X,WANG H.Corrosion characteristics of low alloy steel under H2S/CO2 environment:experimental analysis and theoretical research[J].Materials letters,2017,209:459-462.
[17]CHOI Y S,NESIC S,LING S.Effect of H2S on the CO2corrosion of carbon steel in acidic solutions[J].Electrochimica acta,2010,56(4):1752-1760.
[18]MU G N,LI X H,QU Q,et al.Molybdate and tungstate as crrosion inhibitors for cold rolling steel in hydrochloric acid solution[J].Corrosion science,2006,48(2):445-459.
[19]LóPEZ D A,PéREZ T,SIMISON S N.The influence of microstructure and chemical composition of carbon and low alloy steels in CO2 corrosion.A state-of-the-art appraisal[J].Materials&design,2003,24(8):561-575.
[20]FAN X,XU L,ZHU J Y,et al.Effects of heat treatment on mechanical properties and CO2 corrosion resistance of3Cr Steel[C]//Corrosion 2015.USA:NACE International,2015.
[21]LI W,XU L,QIAO L,et al.Effect of free Cr content on corrosion behavior of 3Cr steels in a CO2 environment[J].Applied surface science,2017,425:32-45.
[22]NACE SP0775-2018,Preparation,installation,analysis,and interpretation of corrosion coupons in oilfield operations[S].
[23]SUN J B,SUN C,LIN X Q,et al.Effect of chromiumon the corrosion behavior of P110 steels in CO2-H2S environment with high pressure and high temperature[J].Materials,2016,9(3):200.
[24]ZHOU C,ZHENG S,CHEN C,et al.The effect of the partial pressure of H2S on the permeation of hydrogen in low carbon pipeline steel[J].Corrosion science,2013,67(1):184-192.
[25]苏鑫.H2S/CO2环境低铬钢腐蚀产物膜形成机理及氢渗透行为研究[D].青岛:中国石油大学(华东),2013.SU Xin.The formation mechanism of corrosion scale and hydrogen permeation behavior of low chromium steel under H2S/CO2 environment[D].Beijing:China University of Petroleum,2013.
[26]秋兴利,薛玉娜,王荣.3Cr钢在3.5%NaCl溶液中的腐蚀行为[J].材料保护,2014,47(3):12-19.QIU Xing-li,XUE Yu-na,WANG Rong.Corrosion behavior of low chromium steel in 3.5%sodium chloride solution[J].Materials protection,2014,47(3):12-19.
[27]吕祥鸿,赵国仙,王宇,等.低铬抗硫套管的H2S/CO2腐蚀行为研究[J].钢铁研究学报,2010,22(7):23-28.LYU Xiang-hong,ZHAO Guo-xian,WANG Yu,et al.Study on H2S/CO2 corrosion behaviors of low-Cr acid resistant casing steel[J].Journal of iron and steel research,2010,22(7):23-28.
[28]MOHAMMADI A H,NADERI M,IRANMANESH M.Fracture toughness evaluation of 3Cr-1Mo steel from vickers indentation and tensile test data[J].Procedia engineering,2011,10:228-235.
[29]LIU Z,GAO X,DU L,et al.Corrosion behavior of low-alloy steel with martensite/ferrite microstructure at vapor-saturated CO2 and CO2-saturated brine conditions[J].Applied surface science,2015,351:610-623.