油气管道的腐蚀及预测研究
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摘要
随着海洋油气开发产业的快速发展,海港油气管道已成为海洋油气开发过程中不可或缺的重要设备。油气钢管服役环境复杂,由于接触油气介质及海水、土壤等环境,服役过程中面临着内外介质的腐蚀而发生油气泄漏事故。由于油气具有易燃、易爆、易毒性等特点,使得油气钢管因腐蚀而产生的危害较大。对油气钢管的腐蚀行为及腐蚀状态预测进行研究,从而制定出恰当的防护措施,已成为确保管道安全运行的有效手段。
根据服役环境的不同,油气钢管的腐蚀分为管道内壁腐蚀和管道外壁环境腐蚀。本文在分析油气管道腐蚀环境的基础上,以Q235B钢和L245钢为研究对象,采用电化学方法研究了管线钢的内腐蚀行为和外部土壤腐蚀行为,并且基于马尔可夫随机过程研究了油气钢管的腐蚀预测方法。首先,建立马尔可夫链预测模型,分别对管道的外防腐层劣化状态和管壁腐蚀状态进行预测；而后,针对油气管道的维修措施问题引入马尔可夫决策过程,确定了油气管道的最优维修策略。本文围绕油气钢管的腐蚀及预测、决策进行研究,主要研究内容和成果包括以下几个方面：
(1)模拟大连港油气管道内环境,针对油气管道内壁存在硫化物腐蚀的现状,分别考虑了内腐蚀介质中含硫量、环境温度和介质pH值等主要因素的影响,对管线钢的管内腐蚀行为进行了试验研究。结果表明,Q235B钢和L245钢表现出相似的腐蚀行为。随着含硫量的增加,两者的腐蚀速率先增大后减小。在含硫量为20mg/L时,两者的腐蚀速率最大；含硫量较少时,Q235B钢和L245钢出现点蚀现象,含硫量较高时发生均匀腐蚀,且主要腐蚀产物为Fe3S4。在一定程度上,高含硫量对管线钢具有缓蚀作用；不同含硫量中阻抗谱时间常数的变化,与阻抗谱的退化现象相关。同等条件的腐蚀介质中,L245钢的耐蚀性要优于Q235B钢。不同温度及不同pH值模拟溶液中的测量结果表明,管线钢在该介质中的腐蚀过程受阴极控制。
(2)根据大连港油气管道附近土壤采样分析,模拟饱和水土壤介质,建立“管线钢—土壤”腐蚀环境,对管线钢的土壤腐蚀行为进行了试验研究。结果表明,Q235B钢比L245钢具有更高的热力学稳定性,但L245钢的耐蚀性要优于Q235B钢,这与两者本身材料的差异性相关。腐蚀前期,两者的电化学阻抗谱均表现为高频区出现小容抗、中频区出现大容抗和低频区出现小感抗；腐蚀后期,低频区小感抗表现出逐渐退化至消失的特征。测量期间Q235B钢的腐蚀速率呈现随时间先增大后缓慢递减的趋势,L245钢的腐蚀速率呈现随时间先缓慢减小后急剧减小的趋势。
(3)基于马尔可夫过程的随机理论,建立油气管道外防腐层劣化状态预测方法。根据外防腐层质量状态评价标准划分外防腐层劣化状态,分别建立了单一管段外防腐层劣化状态预测模型和整条管线外防腐层劣化状态分布预测模型。根据外防腐层检测数据确定其初始状态分布,进而求解转移概率矩阵,分别预测了单一管段外防腐层劣化状态及整条管线外防腐层劣化状态分布的发展趋势。
(4)基于马尔可夫过程的随机理论,建立油气钢管管壁腐蚀状态预测方法。根据管体腐蚀损伤评价标准划分管壁腐蚀状态,分别建立了单一管段管壁腐蚀状态预测模型和整条管线管壁腐蚀状态分布预测模型。通过曲线拟合、灰色—马尔可夫链模型分别确定了单一管段和整条管线管壁腐蚀状态的转移概率矩阵,预测了单一管段和整条管线的管壁腐蚀状态发展趋势。
(5)基于马尔可夫决策过程探究油气管道的维修策略。在确定油气管道维修过程中的腐蚀状态划分以后,分析了油气管道的维修措施及相应费用,并采用策略改进算法对马尔可夫决策过程进行求解。在马尔可夫决策过程应用中,结合一条实际运行油气管线,从腐蚀状态划分、维修措施及费用、不同维修策略下转移概率矩阵的计算及马尔可夫决策过程求解等方面进行了深入探讨,制定了该管线的最优维修策略。
Seaport oil-gas pipelines have become indispensable equipments for the exploitation of oil and gas with the fast development of ocean oil-gas industry. The service environment of oil and gas steel pipelines are complex. It is common reported that oil and gas leakage accidents were happened because of exposing to oil and gas medium or soil environment, which makes the hazard of tube corrosion more greater due to their easy flammable, explosive and toxic feature. Therefore, basing on the research of corrosion behavior and corrosion state prediction for oil and gas steel pipelines, then making out appropriate protective measures, which has become effective means for oil and gas pipeline's safety operation.
According to different service environment, the corrosion of oil and gas steel pipelines are divided into two groups:pipe inner wall corrosion and pipe exine environment corrosion. Basing on the analysis of corrosion environment for oil and gas steel pipelines, taking Q235B steel and L245 steel for research objects, the internal and exine soil corrosion behavior of steel pipelines are studied by means of electrochemical methods. Moreover, the corrosion prediction models are researched basing on the Markov stochastic process. First, Markov chain prediction models are built, which are used to predicting aging conditions for external anticorrosion and pipe wall corrosion damage. Forthermore, Markov decision is introduced in view of maintenance measures for oil and gas steel pipelines, then optimal maintenance strategy is determined. In this paper, centering on the research of corrosion, prediction and its strategic decision for oil and gas steel pipelines. The following are the main contribution of this thesis:
(1) Experimental research is conducted on corrosion behaviors for steel pipelines(Q235B steel and L245 steel) inner wall in the oil-gas simulated internal environment of dalian port. The sulphur content, environment temperature and pH values of corrosion medium are considered in view of existing the present situation with sulfide corrosion in oil and gas steel pipelines inner wall. The results find that Q235B steel and L245 steel show similar corrosion behavior. In the corrosion medium, Corrosion rates of them first increase then decrease with the increase of sulphur content. The corrosion rate have the maximum value when the sulphur content is 20mg/L. Q235B steel and L245 steel occur pitting corrosion phenomenon when the sulphur content is low, while general corrosion happened in the high sulphur content, and the main corrosion product is ferriferous sulfide. The change of time constant of impedance spectroscopy in solutions with different sulphur content that is related to aseptic degeneration of impedance spectroscopy. High sulphur extent has a corrosion inhibiting effect to the steel pipelines in a certain extent. The corrosion resisting property of L245 steel is more stronger than Q235B steel in the same corrosion condition. The results of solutions with different temperatures and pH values show that corrosion processes in the corrosion medium are controlled by the cathode process.
(2) According to sampling and analysis for dalian port soil near the oil-gas pipe, experimental research is conducted on corrosion behaviors for steel pipelines(Q235B steel and L245 steel) in simulated water saturated soil environment of dalian port. The results find that the thermodynamic stability of Q235B steel is higher than L245 steel, while the corrosion resisting property of L245 steel is much stronger than Q235B steel in this condition, which is related to diversity of their nature of materials. At early stage, both of their electrochemical impedance spectroscopy is shown that high-frequency region appears small capacitive reactance, medium-frequency region appears large capacitive reactance and low-frequency region appears little inductive reactance. At later stage, the low-frequency little inductive reactance has become degradation into disappearance gradually. Moreover, the corrosion velocity of Q235B steel increases first then decreases progressively, while the corrosion velocity of L245 steel decreases progressively then decreases rapidly during the measurement period.
(3) The prediction method for extrrnal coating deterioration state of oil-gas pipelines is established based on Markov process stochastic theory. The prediction model of extrrnal coating deterioration state for a single pipe section and the entire pipeline are established respectively according to classification criteria quality status for extrrnal coating. Their initial state distribution are defined based on inspection data of extrrnal coating, then transition probability matrixes are obtained, and finally the trends of extrrnal coating deterioration state for a single pipe section and the entire pipeline are predicted respectively.
(4) The prediction method for tube wall corrosion state of oil-gas steel pipelines is established based on Markov process stochastic theory. The prediction model of tube wall corrosion state for a single pipe section and the entire pipeline are established respectively according to classification criteria quality status for pipe body. The tube wall transition probability matrixes of a single pipe section and the entire pipeline are obtained by curve fitting and gray Markov chain model respectively. Furthermore, the trends of tube wall deterioration state for a single pipe section and the entire pipeline are predicted seperately.
(5) The optimum maintenance strategy of oil-gas pipelines is studied basing on Markov decision process. Maintenance measures and their corresponding cost are analyzed after dividing the corrosion state during oil-gas pipelines'maintenance, and Markov decision process is solved by appling strategy improvement algorithm. The division of corrosion state, maintenance measures and their corresponding cost, the obtaining of transition probability matrixes and the solving of Markov decision process are discussed, which combines with a oil-gas pipeline under service during the application of Markov decision process. Finally, the optimum maintenance strategy for the pipeline is worked out.
根据服役环境的不同,油气钢管的腐蚀分为管道内壁腐蚀和管道外壁环境腐蚀。本文在分析油气管道腐蚀环境的基础上,以Q235B钢和L245钢为研究对象,采用电化学方法研究了管线钢的内腐蚀行为和外部土壤腐蚀行为,并且基于马尔可夫随机过程研究了油气钢管的腐蚀预测方法。首先,建立马尔可夫链预测模型,分别对管道的外防腐层劣化状态和管壁腐蚀状态进行预测；而后,针对油气管道的维修措施问题引入马尔可夫决策过程,确定了油气管道的最优维修策略。本文围绕油气钢管的腐蚀及预测、决策进行研究,主要研究内容和成果包括以下几个方面：
(1)模拟大连港油气管道内环境,针对油气管道内壁存在硫化物腐蚀的现状,分别考虑了内腐蚀介质中含硫量、环境温度和介质pH值等主要因素的影响,对管线钢的管内腐蚀行为进行了试验研究。结果表明,Q235B钢和L245钢表现出相似的腐蚀行为。随着含硫量的增加,两者的腐蚀速率先增大后减小。在含硫量为20mg/L时,两者的腐蚀速率最大；含硫量较少时,Q235B钢和L245钢出现点蚀现象,含硫量较高时发生均匀腐蚀,且主要腐蚀产物为Fe3S4。在一定程度上,高含硫量对管线钢具有缓蚀作用；不同含硫量中阻抗谱时间常数的变化,与阻抗谱的退化现象相关。同等条件的腐蚀介质中,L245钢的耐蚀性要优于Q235B钢。不同温度及不同pH值模拟溶液中的测量结果表明,管线钢在该介质中的腐蚀过程受阴极控制。
(2)根据大连港油气管道附近土壤采样分析,模拟饱和水土壤介质,建立“管线钢—土壤”腐蚀环境,对管线钢的土壤腐蚀行为进行了试验研究。结果表明,Q235B钢比L245钢具有更高的热力学稳定性,但L245钢的耐蚀性要优于Q235B钢,这与两者本身材料的差异性相关。腐蚀前期,两者的电化学阻抗谱均表现为高频区出现小容抗、中频区出现大容抗和低频区出现小感抗；腐蚀后期,低频区小感抗表现出逐渐退化至消失的特征。测量期间Q235B钢的腐蚀速率呈现随时间先增大后缓慢递减的趋势,L245钢的腐蚀速率呈现随时间先缓慢减小后急剧减小的趋势。
(3)基于马尔可夫过程的随机理论,建立油气管道外防腐层劣化状态预测方法。根据外防腐层质量状态评价标准划分外防腐层劣化状态,分别建立了单一管段外防腐层劣化状态预测模型和整条管线外防腐层劣化状态分布预测模型。根据外防腐层检测数据确定其初始状态分布,进而求解转移概率矩阵,分别预测了单一管段外防腐层劣化状态及整条管线外防腐层劣化状态分布的发展趋势。
(4)基于马尔可夫过程的随机理论,建立油气钢管管壁腐蚀状态预测方法。根据管体腐蚀损伤评价标准划分管壁腐蚀状态,分别建立了单一管段管壁腐蚀状态预测模型和整条管线管壁腐蚀状态分布预测模型。通过曲线拟合、灰色—马尔可夫链模型分别确定了单一管段和整条管线管壁腐蚀状态的转移概率矩阵,预测了单一管段和整条管线的管壁腐蚀状态发展趋势。
(5)基于马尔可夫决策过程探究油气管道的维修策略。在确定油气管道维修过程中的腐蚀状态划分以后,分析了油气管道的维修措施及相应费用,并采用策略改进算法对马尔可夫决策过程进行求解。在马尔可夫决策过程应用中,结合一条实际运行油气管线,从腐蚀状态划分、维修措施及费用、不同维修策略下转移概率矩阵的计算及马尔可夫决策过程求解等方面进行了深入探讨,制定了该管线的最优维修策略。
Seaport oil-gas pipelines have become indispensable equipments for the exploitation of oil and gas with the fast development of ocean oil-gas industry. The service environment of oil and gas steel pipelines are complex. It is common reported that oil and gas leakage accidents were happened because of exposing to oil and gas medium or soil environment, which makes the hazard of tube corrosion more greater due to their easy flammable, explosive and toxic feature. Therefore, basing on the research of corrosion behavior and corrosion state prediction for oil and gas steel pipelines, then making out appropriate protective measures, which has become effective means for oil and gas pipeline's safety operation.
According to different service environment, the corrosion of oil and gas steel pipelines are divided into two groups:pipe inner wall corrosion and pipe exine environment corrosion. Basing on the analysis of corrosion environment for oil and gas steel pipelines, taking Q235B steel and L245 steel for research objects, the internal and exine soil corrosion behavior of steel pipelines are studied by means of electrochemical methods. Moreover, the corrosion prediction models are researched basing on the Markov stochastic process. First, Markov chain prediction models are built, which are used to predicting aging conditions for external anticorrosion and pipe wall corrosion damage. Forthermore, Markov decision is introduced in view of maintenance measures for oil and gas steel pipelines, then optimal maintenance strategy is determined. In this paper, centering on the research of corrosion, prediction and its strategic decision for oil and gas steel pipelines. The following are the main contribution of this thesis:
(1) Experimental research is conducted on corrosion behaviors for steel pipelines(Q235B steel and L245 steel) inner wall in the oil-gas simulated internal environment of dalian port. The sulphur content, environment temperature and pH values of corrosion medium are considered in view of existing the present situation with sulfide corrosion in oil and gas steel pipelines inner wall. The results find that Q235B steel and L245 steel show similar corrosion behavior. In the corrosion medium, Corrosion rates of them first increase then decrease with the increase of sulphur content. The corrosion rate have the maximum value when the sulphur content is 20mg/L. Q235B steel and L245 steel occur pitting corrosion phenomenon when the sulphur content is low, while general corrosion happened in the high sulphur content, and the main corrosion product is ferriferous sulfide. The change of time constant of impedance spectroscopy in solutions with different sulphur content that is related to aseptic degeneration of impedance spectroscopy. High sulphur extent has a corrosion inhibiting effect to the steel pipelines in a certain extent. The corrosion resisting property of L245 steel is more stronger than Q235B steel in the same corrosion condition. The results of solutions with different temperatures and pH values show that corrosion processes in the corrosion medium are controlled by the cathode process.
(2) According to sampling and analysis for dalian port soil near the oil-gas pipe, experimental research is conducted on corrosion behaviors for steel pipelines(Q235B steel and L245 steel) in simulated water saturated soil environment of dalian port. The results find that the thermodynamic stability of Q235B steel is higher than L245 steel, while the corrosion resisting property of L245 steel is much stronger than Q235B steel in this condition, which is related to diversity of their nature of materials. At early stage, both of their electrochemical impedance spectroscopy is shown that high-frequency region appears small capacitive reactance, medium-frequency region appears large capacitive reactance and low-frequency region appears little inductive reactance. At later stage, the low-frequency little inductive reactance has become degradation into disappearance gradually. Moreover, the corrosion velocity of Q235B steel increases first then decreases progressively, while the corrosion velocity of L245 steel decreases progressively then decreases rapidly during the measurement period.
(3) The prediction method for extrrnal coating deterioration state of oil-gas pipelines is established based on Markov process stochastic theory. The prediction model of extrrnal coating deterioration state for a single pipe section and the entire pipeline are established respectively according to classification criteria quality status for extrrnal coating. Their initial state distribution are defined based on inspection data of extrrnal coating, then transition probability matrixes are obtained, and finally the trends of extrrnal coating deterioration state for a single pipe section and the entire pipeline are predicted respectively.
(4) The prediction method for tube wall corrosion state of oil-gas steel pipelines is established based on Markov process stochastic theory. The prediction model of tube wall corrosion state for a single pipe section and the entire pipeline are established respectively according to classification criteria quality status for pipe body. The tube wall transition probability matrixes of a single pipe section and the entire pipeline are obtained by curve fitting and gray Markov chain model respectively. Furthermore, the trends of tube wall deterioration state for a single pipe section and the entire pipeline are predicted seperately.
(5) The optimum maintenance strategy of oil-gas pipelines is studied basing on Markov decision process. Maintenance measures and their corresponding cost are analyzed after dividing the corrosion state during oil-gas pipelines'maintenance, and Markov decision process is solved by appling strategy improvement algorithm. The division of corrosion state, maintenance measures and their corresponding cost, the obtaining of transition probability matrixes and the solving of Markov decision process are discussed, which combines with a oil-gas pipeline under service during the application of Markov decision process. Finally, the optimum maintenance strategy for the pipeline is worked out.
引文
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