赵国仙,刘冉冉,李琼玮,杨立华,孙雨来,丁浪勇,王映超,张思琦,宋洋.5Cr油套管钢在含Cl−的CO2环境中的腐蚀特性研究[J].表面技术,2024,53(6):55-66.
ZHAO Guoxian,LIU Ranran,LI Qiongwei,YANG Lihua,SUN Yulai,DING Langyong,WANG Yingchao,ZHANG Siqi,SONG Yang.Corrosion Characteristics of 5Cr Oil Casing Steel in Cl−-containing CO2 Environment[J].Surface Technology,2024,53(6):55-66
5Cr油套管钢在含Cl−的CO2环境中的腐蚀特性研究
Corrosion Characteristics of 5Cr Oil Casing Steel in Cl−-containing CO2 Environment
投稿时间:2023-03-27  修订日期:2023-11-06
DOI:10.16490/j.cnki.issn.1001-3660.2024.06.005
中文关键词:  5Cr油套管钢  CO2腐蚀  腐蚀产物膜  Cr元素富集  电化学阻抗谱  丝束电极
英文关键词:5Cr oil casing steel  CO2 corrosion  corrosion product film  Cr element enrichment  electrochemical impedance spectroscopy  wire beam electrode
基金项目:
作者单位
赵国仙 西安石油大学 材料科学与工程学院,西安 710065 
刘冉冉 西安石油大学 材料科学与工程学院,西安 710065 
李琼玮 长庆油田分公司油气工艺研究院,西安 710018;低渗透油气田勘探开发国家工程实验室,西安 710018 
杨立华 长庆油田分公司油气工艺研究院,西安 710018;低渗透油气田勘探开发国家工程实验室,西安 710018 
孙雨来 长庆油田分公司油气工艺研究院,西安 710018;低渗透油气田勘探开发国家工程实验室,西安 710018 
丁浪勇 西安石油大学 材料科学与工程学院,西安 710065 
王映超 西安石油大学 材料科学与工程学院,西安 710065 
张思琦 西安摩尔石油工程实验室股份有限公司,西安 710065 
宋洋 西安摩尔石油工程实验室股份有限公司,西安 710065 
AuthorInstitution
ZHAO Guoxian School of Material Science and Technology, Xi'an Shiyou University, Xi'an 710065, China 
LIU Ranran School of Material Science and Technology, Xi'an Shiyou University, Xi'an 710065, China 
LI Qiongwei Research Institute of Oil & Gas Technology, Changqing Oilfield, Xi'an 710018, China;National Engineering Laboratory for Exploration and Development of Low-Permeability Oil & Gas Field, Xi'an 710018, China 
YANG Lihua Research Institute of Oil & Gas Technology, Changqing Oilfield, Xi'an 710018, China;National Engineering Laboratory for Exploration and Development of Low-Permeability Oil & Gas Field, Xi'an 710018, China 
SUN Yulai Research Institute of Oil & Gas Technology, Changqing Oilfield, Xi'an 710018, China;National Engineering Laboratory for Exploration and Development of Low-Permeability Oil & Gas Field, Xi'an 710018, China 
DING Langyong School of Material Science and Technology, Xi'an Shiyou University, Xi'an 710065, China 
WANG Yingchao School of Material Science and Technology, Xi'an Shiyou University, Xi'an 710065, China 
ZHANG Siqi Xi'an Moore Petroleum Engineering Laboratory Limited Company, Xi'an 710065, China 
SONG Yang Xi'an Moore Petroleum Engineering Laboratory Limited Company, Xi'an 710065, China 
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中文摘要:
      目的 掌握油气井生产中CO2腐蚀对油套管的影响规律,研究兼顾耐蚀性和经济性的5Cr油套管材料在含Cl的CO2环境中不同时间下的腐蚀演变规律。方法 采用XRD、XPS、SEM和EDS等技术分析5Cr油套管钢在不同时间下腐蚀产物膜的演变情况,利用丝束电极(WBE)和阻抗测试(EIS)技术对其腐蚀电化学行为进行研究。结果 5Cr油套管钢腐蚀后期的平均腐蚀速率约为初期的1/2,在腐蚀14 d后,腐蚀产物膜中的Cr富集大于30%,Cr、Fe质量比达到较高水平,约为基体的15倍。随着腐蚀的进行,电荷传递电阻和产物膜覆盖引起的电阻增大,电化学反应阻力增大。在腐蚀前期具有局部不均匀性,随着腐蚀的进行,电极腐蚀电位有负移现象,最终分布区间为−0.59~−0.61 V,电极表面阳极电流区域大幅减少。结论 在腐蚀时间延长的条件下,5Cr油套管钢腐蚀产物膜的致密性增加,电荷传递电阻呈变大趋势。在产物膜下的5Cr油套管钢区域,电流发生由阴极向阳极极性转变的现象,产物膜存在的孔隙使5Cr油套管钢基体金属被腐蚀,从而导致阳极电流的出现。表面局部腐蚀电位阳极区的形成和扩展使其有产生点蚀的倾向,但腐蚀产物逐渐沉积在点蚀坑内壁,形成了Cr富集的保护性表面层,原发生点蚀区域由原阳极活性点位转变为阴极区,对其发展起到了抑制作用。
英文摘要:
      Wire beam electrode (WBE) technology can accurately describe the corrosion potential and current density distribution of the electrode surface, and EIS technology can obtain the corrosion electrochemical information of the metal substrate under the cover of the corrosion product film, and combine the advantages of the two to study and analyze the CO2 corrosion characteristics of 5Cr oil casing steel at different temperature accurately and in detail. Among them, the corrosion products form a barrier film on the inner wall of the pipeline have a great degree of protection for the pipe body itself and reduce the overall corrosion rate. However, there will be rupture and regeneration of the product film at different stages of corrosion, and the pores of the corrosion product film will cause the active site of the substrate to react, and local corrosion is prone to occur here, and there is a tendency to form pitting corrosion, and the effect of local damage on local corrosion of the substrate has not gotten much enough attention, so it is necessary to study it. The corrosion characteristics of 5Cr oil casing steel in the environment of 0.1 MPa CO2 and 65 g/L Cl− were studied by immersion test and electrochemical test. The corrosion product layer for different corrosion time was analyzed by XRD, XPS, SEM and EDS and the polarization curves and impendence spectroscopy test were used to analyze electrochemical characteristics of 5Cr oil casing steel. The results showed that the corrosion product layer on 5Cr oil casing steel surface was composed of FeCO3 and Cr(OH)3 inlays in inner layer and the grainy CaCO3 in outside layer. After 14 d, the Cr enrichment in the corrosion product layer reached more than 30%, and the mass fraction ratio of Cr/Fe in the product layer reached higher, which was about 15 times of the substrate. As the corrosion progressed, the overall resistance caused by the fitted charge transfer resistance and the product film coverage in the circuit became larger, so that the anode reaction was inhibited, the charge transfer process became more and more difficult, and the resistance of the electrochemical reaction increased significantly. In the early stage of corrosion, there was local inhomogeneity, and with the progress of corrosion, the electrode corrosion potential had a negative shift, and the final distribution range was −0.59-−0.61 V, and the anode current area on the electrode surface was greatly reduced. The capacitive impedance arc with a large radius is formed in the electrochemical impedance spectrum of 5Cr oil casing steel, the film coverage degree and compactness of the corrosion product increase, the resistance caused by the charge transfer resistance in the equivalent circuit tends to increase, and the resistance of the electrochemical reaction increases significantly. The formation and expansion of the local anode zone on the surface of 5Cr oil casing steel have the tendency to cause pitting corrosion, and it is formed at the void channel of the film in the early stage of corrosion. The corrosion products are gradually deposited on the inner wall of the pit, and a protective surface layer with obvious Cr enrichment is formed on the inner wall of the pit, and the original pitting corrosion area is transformed from the original anode active point to the cathode area, which inhibits its development. The polar transformation phenomenon of the 5Cr oil casing steel area current under the corrosion product film occurs from the cathode to the anode, and the pores in the product film make the 5Cr oil casing steel base metal corroded, resulting in the appearance of anode current.
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