油套管二氧化碳腐蚀研究
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摘要
CO_2驱油增产技术的广泛应用以及一些油气田采出液中本身所含有的CO_2,使得CO_2腐蚀成为困扰油气生产的一个主要问题。油气生产和运输使用的管线钢遭受CO_2腐蚀后,力学性能降低,使用寿命缩短,特别在设备发生CO_2局部腐蚀后,产生凹坑甚至穿孔,破坏更为严重。因此,研究CO_2腐蚀机理、腐蚀速率预测模型,分析设备遭受CO_2腐蚀后失效和破坏的原因,具有重要的工程应用价值。
本文从腐蚀电化学着手,将油气田CO_2腐蚀进程分为三个阶段,指出扩散层传质过程是整个均匀腐蚀进程的速度控制步骤,在此基础上,利用极限扩散电流,推导出均匀腐蚀预测模型,并分析了影响CO_2均匀腐蚀的主要因素;CO_2腐蚀产物膜与腐蚀进程密切相关,总结国内外CO_2腐蚀产物膜的研究成果,分析研究得出腐蚀产物膜的形成过程;腐蚀产物膜破坏是发生局部腐蚀的诱导原因,但不同的局部腐蚀类型,具有不同的动力增长机理:点蚀可看做较低pH值下的均匀腐蚀,而流动诱导腐蚀和台面腐蚀受电极反应的放电步骤控制;推导出局部腐蚀速率预测模型,为油气田实际应用提供参考;油管发生CO_2局部腐蚀后,腐蚀穿孔失效,甚至在交变载荷作用下疲劳破坏,发生掉井;套管发生CO_2局部腐蚀后,在外压或内外压作用下,腐蚀凹坑处应力集中,达到屈服极限,发生破坏。
With wide application of carbon dioxide injection technology to improve oil recovery and the produced liquid of some oil-gas field contains carbon dioxide, carbon dioxide corrosion become a main problem of oil-gas production. Mechanical properties and service-span of Pipeline equipment for oil-gas production and transportation decrease, especial localized corroded equipment are more likely to be damaged. So, it is very important to research the mechanism of carbon dioxide corrosion, the corrosion rate prediction model and analyze corrosion failure of the equipment.
This thesis analyzes carbon dioxide corrosion using corrosion electrochemistry method and divide corrosion process into three steps, state that transmission process in diffusion layer control the whole general corrosion, deduct general corrosion rate prediction model, analyze the main factors which influence carbon dioxide corrosion; Corrosion product film is associate with corrosion process, after summing up research results of corrosion produce film home and abroad, analyze the corrosion product film forming process; The damage of corrosion product film induce localized corrosion and different localized corrosion style has different drive mechanism; Pitting corrosion can be considered to be general corrosion in low pH condition, flow induced corrosion and mesa type corrosion are controlled by the rate of electrode reaction; Deduct a localized corrosion rate prediction model which is useful for oil-gas field; Localized corroded tube are fatigue failure under alternating loads; Corroded casing damage when stress concentration excel yield limit at corrosion pit under external pressure or external and internal pressure.
本文从腐蚀电化学着手,将油气田CO_2腐蚀进程分为三个阶段,指出扩散层传质过程是整个均匀腐蚀进程的速度控制步骤,在此基础上,利用极限扩散电流,推导出均匀腐蚀预测模型,并分析了影响CO_2均匀腐蚀的主要因素;CO_2腐蚀产物膜与腐蚀进程密切相关,总结国内外CO_2腐蚀产物膜的研究成果,分析研究得出腐蚀产物膜的形成过程;腐蚀产物膜破坏是发生局部腐蚀的诱导原因,但不同的局部腐蚀类型,具有不同的动力增长机理:点蚀可看做较低pH值下的均匀腐蚀,而流动诱导腐蚀和台面腐蚀受电极反应的放电步骤控制;推导出局部腐蚀速率预测模型,为油气田实际应用提供参考;油管发生CO_2局部腐蚀后,腐蚀穿孔失效,甚至在交变载荷作用下疲劳破坏,发生掉井;套管发生CO_2局部腐蚀后,在外压或内外压作用下,腐蚀凹坑处应力集中,达到屈服极限,发生破坏。
With wide application of carbon dioxide injection technology to improve oil recovery and the produced liquid of some oil-gas field contains carbon dioxide, carbon dioxide corrosion become a main problem of oil-gas production. Mechanical properties and service-span of Pipeline equipment for oil-gas production and transportation decrease, especial localized corroded equipment are more likely to be damaged. So, it is very important to research the mechanism of carbon dioxide corrosion, the corrosion rate prediction model and analyze corrosion failure of the equipment.
This thesis analyzes carbon dioxide corrosion using corrosion electrochemistry method and divide corrosion process into three steps, state that transmission process in diffusion layer control the whole general corrosion, deduct general corrosion rate prediction model, analyze the main factors which influence carbon dioxide corrosion; Corrosion product film is associate with corrosion process, after summing up research results of corrosion produce film home and abroad, analyze the corrosion product film forming process; The damage of corrosion product film induce localized corrosion and different localized corrosion style has different drive mechanism; Pitting corrosion can be considered to be general corrosion in low pH condition, flow induced corrosion and mesa type corrosion are controlled by the rate of electrode reaction; Deduct a localized corrosion rate prediction model which is useful for oil-gas field; Localized corroded tube are fatigue failure under alternating loads; Corroded casing damage when stress concentration excel yield limit at corrosion pit under external pressure or external and internal pressure.
引文
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[3]De Waard C.,Milliams D.E..Prediction of Carbonic Acid Corrosion in Natural Gas Pipelines[J].Corrosion,1975,31(5):177
[4]Hausler R.H.,Stegmann D.W..CO_2 Corrosion and Its Prevention by Chemical Inhibition in Oil and Gas Production[J].Corrosion,1988,44(1):5-9
[5]Davies D.H.,Burstein G.T.,The effects of Bicarbonate on the Corrosion and Passivation of Iron Corrosion[J].Corrosion,1980,36(8):416-422
[6]Rahmel A.,Schwenk W..Korrosion und Korrosionsschutz von St(a|¨)hlen[M].Weinheim,New York,1977,105-110
[7]Ogundele G.L.,White.Some Observations on Corrosion of Carbon Steel in Aquecus Environments Containing Carbon Dioxide[J].Corrosion,1986,42(2):71
[8]Xia Z.,Chou K.C..Piting Corrosion of Carbon Steel in CO_2 Containing NaCl Brine[J].Corrosion,1989,45(8):636
[9]Nesic S.,Postlethwaite J..An Electrochemical Model for Prediction of Corrosion of Mild Steel in Squcous Carbon Dioxide Solutions[J].Corrosion,1996,52(4):280
[10]Schmit G.,Fundamental Aspects of CO_2 Corrosion[R].Houston:NACE International,1983
[11]Ikeda A.,Ueda M.,Mukai S..Advances in CO_2 Corrosion[R].Houston,NACE International,1984
[12]Schmitt G.CO_2 Corrosion of Steels an Attempt to Range Parameter and Their Effects[A].In:Hausler R H.Giddard H P(Eds),Advances in CO_2 Corrosion[C].Houslon:NACE International,1984:10-13
[13]Onsrud G.,Sontvedt T..Recording of Local Flow Disturbances Behind Obstacles Where Mesa Attack have Occurred[A].Corrosion[C].Houston:NACE International,1998,40-43
[14]Nyborg R..Initiation and Growth of Mesa Corrosion Attack During CO_2 Corrosion of Carbon Steel[A].Corrosion[C].Houston:NACE International,1998,48-50
[15]Crolet J.L.,Thevenot N.,Nesic S..Role of Conductive Corrosion Products on the Protectiveness of Corrosion Layers[A].Corrosion[C].Houston:NACE International 1996,4-6
[16]张清,李全安,文九巴等.压力与油管钢CO_2/H_2S腐蚀速率的关系[J].焊管,2005,28(5):24-27
[17]张清,李全安,文九巴等.CO_2分压对油管钢腐蚀产物膜的影响[J].石油机械,2004,32(4):13-14
[18]林冠发,白真权,赵新伟等.CO_2腐蚀产物膜形态结构与温度和压力的关系[J].石油机械,2005,33(2):1-4
[19]陈长风,路民旭,赵国仙等.温度、Cl~-浓度、Cr元素对N80钢CO_2腐蚀电极过程的影响[J].金属学报,2003,39(8):848-854
[20]陈长风,金瑞萍,李群智等.温度对管线钢CO_2腐蚀产物膜结构的影响[J].防护保温技术,2005,13(4):15-22
[21]龙凤乐,郑文军,陈长风等.温度、CO_2分压、流速、pH值对X65管线钢CO_2均匀腐蚀速率的影响规律[J].腐蚀与防护,2005,26(7):90-94
[22]Palacios C.A.,Shadley J.R..Characteristic of Corrosion Scales on Steels in CO_2Saturated NaCl Brine[J].Corrosion,1991,47(2):122-127
[23]陈长风,路民旭,赵国仙等.N80油套钢CO_2腐蚀产物膜特征[J].金属学报,2002,38(4):411-416
[24]Ikeda A.,Ueda M..Predicting CO_2 Corrosion in the Oil and Gas Industry[M].London:The Institute of Materials,1994,59-63
[25]郑家燊,吕战鹏.二氧化碳腐蚀机理及影响因素[J].石油学报,1995,16(3):134-139
[26]林冠发,郑茂盛,白真权等.P110钢CO_2腐蚀产物膜的XPS分析[J].光谱学与光谱分析,2005,25(11):1875-1879
[27]Dayalan E.,Vani G.,Shadley J.R.et al.Erosion Corrosion of a Carbon Steel Elbow in a Carbon Dioxide Environment[J].Corrosion,1996,52:714-723
[28]Wu S.L.,Cui Z.D.,Zhao G.X.et al.EIS Study of the Surface film on the Surface of Carbon Steel from Supercritical Carbon Dioxide Corrosion[J].Applied Surface Science.2004,228(1-4),17-25
[29]Mora-Mendoza J.L.,Turgoose S..Fe_3C Influence on the Corrosion Rate of Mild Steel in Aqueous CO_2 Systems under Turbulent Flow Conditions[J],Corrosion Science. 2002,44(6):1223-1246
[30]杜海燕,路民旭,吴荫顺等.油酸酰胺的合成及其性能研究[J].腐蚀科学与防护技术,2006,18(5):370-373
[31]黄金营,魏慧芳,张利嫱等.咪唑啉油酰胺的合成及在油气井产出液中的缓蚀性能[J].油田化学,004,21(3):230-233
[32]张锡波,林文兴.肯西油田的井下腐蚀与化学防腐蚀[J].油田化学,2001,18(3):235-237
[33]马涛,张贵才,葛际江等.改性咪唑啉缓蚀剂的合成与评价[J].石油与天然气化工,2004,33(5):359-361
[34]王业飞,由庆,赵福麟.一种新型咪唑啉复配缓蚀剂对A3钢在饱和CO_2盐水中的缓蚀性能[J].石油学报,2006,22(3):74-78
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