天然气工业2024,Vol.44Issue(11) :161-169.DOI:10.3787/j.issn.1000-0976.2024.11.015

H2S/CO2共存环境中X65钢点腐蚀形成机理及预测方法

Formation mechanism and prediction method of pitting corrosion of X65 steel in H2S/CO2 coexistent environment

闫伟 刘琬晴 李光聪 张晨 邹子琛 Srdjan Nesic
天然气工业2024,Vol.44Issue(11) :161-169.DOI:10.3787/j.issn.1000-0976.2024.11.015

H2S/CO2共存环境中X65钢点腐蚀形成机理及预测方法

Formation mechanism and prediction method of pitting corrosion of X65 steel in H2S/CO2 coexistent environment

闫伟 1刘琬晴 1李光聪 1张晨 1邹子琛 1Srdjan Nesic2
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作者信息

  • 1. 中国石油大学(北京)安全与海洋工程学院;油气生产安全与应急技术应急管理部重点实验室·中国石油大学(北京)
  • 2. 油气生产安全与应急技术应急管理部重点实验室·中国石油大学(北京);美国俄亥俄大学腐蚀与多相流研究所
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摘要

碳钢管材广泛应用于油气生产系统,在含CO2、H2S、氯离子等多种腐蚀介质共存的多相流环境中,容易发生腐蚀穿孔泄漏,可能造成管道和设备的失效,进而带来安全隐患和经济损失.目前针对H2S/CO2共存环境下金属腐蚀的研究主要集中在较高H2S分压下,多种形式FeS产物的生成规律、产物膜保护特性和点蚀形成机理,很少研究极微量H2S诱发点腐蚀的可能性和发生条件.为此,以X65钢为例,利用大型H2S多相流腐蚀环路实验系统完成了 4组测试实验和2组验证实验,研究了 40 ℃、恒定CO2分压环境下,不同H2S分压对低碳钢点腐蚀行为的影响规律,并提出了一种基于热力学理论的预测方法.研究结果表明:①当H2S分压高于50 Pa时,X65钢的腐蚀速率低且表现为全面腐蚀;而当H2S分压低于24 Pa时,随着H2S分压的逐步降低,X65钢的点腐蚀加剧,H2S为2.4 Pa时的点腐蚀速率超过11 mm/a.②当H2S分压极低且马基诺型FeS的过饱和度低于1时,快速形成的FeS膜不能完整覆盖金属表面,暴露表面会在电偶腐蚀的作用下,被饱和CO2溶液快速腐蚀,最终导致低碳钢发生局部点腐蚀.③建立不同H2S分压下低碳钢表面马基诺型FeS过饱和度边界控制曲线,可以准确预测不同条件下碳钢的点腐蚀行为.结论认为,在相关行业标准规定的H2S分压下限以内,H2S/CO2共存环境中极微量的H2S仍然可能会诱发碳钢发生点腐蚀,该认识对于H2S/CO2共存环境下油气管道的局部点腐蚀预测和防腐防护研发具有重要理论和现实意义.

Abstract

Carbon steel pipes are widely used in oil and gas production systems,and they are susceptible to corrosion,perforation and leakage in multiphase flow environments containing various corrosive media such as CO2,H2S,and Cl-.This may cause pipeline and equipment failure,thus leading to safety hazards and economic losses.At present,researches on the metal corrosion in H2S/CO2 coexistent environments mainly focus on the formation laws of various FeS products,the protective performances of product films,and the formation mechanisms of pitting corrosion under high H2S partial pressures,but seldom on the possibility and occurrence conditions of pitting corrosion induced by extremely trace amount of H2S.Taking X65 steel as an example,this paper carries out 4 sets of testing experiments and 2 sets of verification experiments by using the large-scale H2S multiphase flow corrosion loop experimental system,studies the influence of different H2S partial pressures on the pitting corrosion behavior of low carbon steel under 40 ℃ and constant CO2 partial pressure,and proposes a prediction method based on the thermodynamic theory.The following results are obtained.First,when the H2S partial pressure is higher than 50 Pa,X65 steel undergoes general corrosion with a low corrosion rate.When it is lower than 24 Pa,with its gradual decreasing,pitting corrosion of X65 steel intensifies,with the pitting corrosion rate exceeding 11 mm/a at 2.4 Pa of H2S partial pressure.Second,when it is extremely low and the supersaturation of Mackinawite type FeS is less than 1,the rapidly formed FeS film cannot fully cover the metal surface.Thereby under the action of galvanic corrosion,the exposed surface is rapidly corroded by saturated CO2 solution,and ultimately local pitting corrosion occurs on low carbon steel.Third,the supersaturation boundary control curve of the Mackinawite type FeS on the surface of low carbon steel under different H2S partial pressures is helpful in the accurate prediction of pitting corrosion behaviors of carbon steel under different conditions.In conclusion,within the lower limit of H2S partial pressure specified in relevant industry standards,even trace amount of H2S in H2S/CO2 coexistent environments may still induce pitting corrosion on carbon steel.This understanding is of important theoretical and practical significance for the prediction and prevention of local pitting corrosion on oil and gas pipelines in H2S/CO2 coexistent environments.

关键词

H2S/CO2/共存环境/低碳钢/点腐蚀/腐蚀机理/预测方法

Key words

H2S/CO2/Coexistent environment/Low carbon steel/Pitting corrosion/Corrosion mechanism/Prediction method

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出版年

2024
天然气工业
四川石油管理局 中国石油西南油气田公司 中国石油川庆钻探工程公司

天然气工业

CSTPCD北大核心EI
影响因子:2.298
ISSN:1000-0976
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