金属及涂装体系在化工大气环境下腐蚀行为研究
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摘要
近年来,随着我国国民经济的快速发展,能源消耗加大,对石油的依赖性增强,而我国原油资源相对短缺,深度开采使得原油劣质化倾向严重,进口原油多为高硫、高酸原油,因此石化行业大气中腐蚀性气体含量日趋升高,设备装置腐蚀问题越来越严重。目前我国石化行业中除了对钢质管道、储罐的防护技术提出了相关规定要求外,对其他设备、设施尚未有规范、规程和标准可循,因此,研究金属及涂装体系在化工大气环境下的腐蚀行为,了解不同金属及涂装体系的腐蚀规律和耐蚀特性,对于合理选择防护措施,延长设备、材料使用寿命,减少腐蚀造成的经济损失,不仅有重要的意义,而且有广泛的应用价值。
本文采用Q235碳钢、铜、铝和锌四种金属以及20种涂装体系,在石化厂区脱硫反应塔、测试中心和武汉大气环境材料腐蚀国家野外科学观测研究站三个暴露点进行大气暴露试验,用SEM和XRD等对锈层和腐蚀产物进行分析；在实验室用中性盐雾加速试验以及老化试验研究了涂装体系的耐候性以及耐蚀性,并探究了薄液膜下Q235碳钢的电化学腐蚀行为规律。
研究表明,石化厂区大气环境对材料的腐蚀是一个复杂的过程。金属材料在脱硫反应塔研究站腐蚀速率高于另外两个站,其中Q235碳钢在脱硫反应塔腐蚀极其严重,腐蚀速率达到C5级别,另外两个研究站为C3级；涂装体系经过室外暴露结果和室内加速结果比对,喷铝涂层耐蚀性好,氟碳面漆耐候性优异,以富锌以及喷铝为底漆的体系耐蚀性能好。
三个研究站点碳钢锈层形态各异,腐蚀产物也各不相同,腐蚀产物的成长对基体具有一定的保护作用。碳钢在石化厂区腐蚀并不是呈现均匀腐蚀,锈层与基体之间有缝隙,由一年腐蚀断面线扫描图可以看到,锈层中的硫元素的含量很低。碳钢在石化厂区初期为大量隆起状颗粒,随着腐蚀的进一步发生,颗粒连接为整片的锈层,但锈层具有裂纹,并不能完全阻碍腐蚀的产生。
在含有氯离子、硫酸根离子以及两者混合同浓度离子的薄液膜下,氯离子对碳钢腐蚀影响作用较硫酸根离子的强。研究了各液膜厚度下Q235碳钢在各浓度硫酸钠溶液中的腐蚀速率,表明：随着液膜厚度的增大,腐蚀速率先减小后增大；不同浓度下Q235碳钢的腐蚀速率规律各不同。在7μm薄液膜下,腐蚀速率随浓度增大而减小。而在其余测试厚度薄液膜及本体溶液中,腐蚀速率则随浓度增大呈现先增大后减小的规律。
In recent years, with the rapid development of national economy, energy consumption increased and the dependence for oil is enhanced, while chinese crude oil resources are relatively short, the deep exploitation makes the tendency of low-grade crude oil serious, and most imported crude oil are high sulfur and high acid, so the content of corrosive gases in petrochemical industry rises day by day, the corrosion problem of equipment is getting more and more serious. At present, there are no standards or regulations of equipment protection teconology except for steel pipelines and storage tanks in national petrochemical industry. Therefore, studying the corrosion behavior of metal and coating system in the petrochemical atmospheric environment, understanding the law of corrosion and corrosion resistance of different metal and coating system, not only have important significance, but also have great value in application, for the reasonable selection of protective measures, prolonging the using life of equipments and materials and reducing the economic loss caused by corrosion.
In this paper, atmospheric exposure tests were carried out in the desulfurization tower, testing centers of the petrochemical plant and atmospheric corrosion of Wuhan National Field Research Stationt with Q235 carbon steel, copper, aluminum, zinc and 20 species of coating system. Rust and corrosion products were analyzed by SEM and XRD. Weatherability and corrosion resistance of the coating system were studied by means of neutral salt spray accelerated test and aging test in laboratories, besides the electrochemical corrosion behavior of the carbon Q235 steel in thin electrolyte film.
The results show that the corrosion of materials in petrochemical atmosphere is a complex process. The corrosion rate of metal in the desulfurization tower research station was higher than the other two stations. The corrosion of Q235 carbon steel in the desulfurization tower was extremely serious, the corrosion rate reached for the C5 level, compared with C3 level in the other two research stations. The characteristics of coating system were compared between outdoor exposure tests and indoor accelerated tests, the results indicated that sprayed aluminum coating has a excellent corrosion resistance, fluorocarbon coating has a great weathering resistance, and zinc-rich and sprayed aluminum primer system possess good corrosion resistance.
The rust layer of carbon steel in the three research sites had a various shapes, and corrosion products were also different, the growth of which had a certain protective function to the substrate. In the petrochemical plant, the corrosion of carbon steel is not uniform corrosion, as there are some cracks between the rust layer and magnesium substrate. We can see that the surful content in the rust layer is very low through the section of line scans. The surface of carbon steel had massive prosperous undulation pellet in the initial period, with the further occurrence of corrosion, the pellets connected for an entire piece of rust layer. However, the corrosion could not be completely hindered, since there were some cracks in the rust layer.
In the thin film containing chloride ion, sulfate ion and the same concentration mixture of the two ions, the chloride ion did a more enormous implication in the corrosion of carbon steel, compared with sulfate ion. The corrosion rate of the Q235 carbon steel in various densities sodium sulfate solution and thin film thickness were studied, the results indicated that:the corrosion rate decreases with the film thickness increases, and then increases; different concentrations of sodium sulfate solution resulted in a different corrosion rate rules. Under the 7μm liquid film, the corrosion rate decreased with the increasing concentration of sodium sulfate solution. In the remaining test of the thin film's thickness and the bulk solution's concentration, the corrosion rate increased with the concentration increased, and then decreased.
本文采用Q235碳钢、铜、铝和锌四种金属以及20种涂装体系,在石化厂区脱硫反应塔、测试中心和武汉大气环境材料腐蚀国家野外科学观测研究站三个暴露点进行大气暴露试验,用SEM和XRD等对锈层和腐蚀产物进行分析；在实验室用中性盐雾加速试验以及老化试验研究了涂装体系的耐候性以及耐蚀性,并探究了薄液膜下Q235碳钢的电化学腐蚀行为规律。
研究表明,石化厂区大气环境对材料的腐蚀是一个复杂的过程。金属材料在脱硫反应塔研究站腐蚀速率高于另外两个站,其中Q235碳钢在脱硫反应塔腐蚀极其严重,腐蚀速率达到C5级别,另外两个研究站为C3级；涂装体系经过室外暴露结果和室内加速结果比对,喷铝涂层耐蚀性好,氟碳面漆耐候性优异,以富锌以及喷铝为底漆的体系耐蚀性能好。
三个研究站点碳钢锈层形态各异,腐蚀产物也各不相同,腐蚀产物的成长对基体具有一定的保护作用。碳钢在石化厂区腐蚀并不是呈现均匀腐蚀,锈层与基体之间有缝隙,由一年腐蚀断面线扫描图可以看到,锈层中的硫元素的含量很低。碳钢在石化厂区初期为大量隆起状颗粒,随着腐蚀的进一步发生,颗粒连接为整片的锈层,但锈层具有裂纹,并不能完全阻碍腐蚀的产生。
在含有氯离子、硫酸根离子以及两者混合同浓度离子的薄液膜下,氯离子对碳钢腐蚀影响作用较硫酸根离子的强。研究了各液膜厚度下Q235碳钢在各浓度硫酸钠溶液中的腐蚀速率,表明：随着液膜厚度的增大,腐蚀速率先减小后增大；不同浓度下Q235碳钢的腐蚀速率规律各不同。在7μm薄液膜下,腐蚀速率随浓度增大而减小。而在其余测试厚度薄液膜及本体溶液中,腐蚀速率则随浓度增大呈现先增大后减小的规律。
In recent years, with the rapid development of national economy, energy consumption increased and the dependence for oil is enhanced, while chinese crude oil resources are relatively short, the deep exploitation makes the tendency of low-grade crude oil serious, and most imported crude oil are high sulfur and high acid, so the content of corrosive gases in petrochemical industry rises day by day, the corrosion problem of equipment is getting more and more serious. At present, there are no standards or regulations of equipment protection teconology except for steel pipelines and storage tanks in national petrochemical industry. Therefore, studying the corrosion behavior of metal and coating system in the petrochemical atmospheric environment, understanding the law of corrosion and corrosion resistance of different metal and coating system, not only have important significance, but also have great value in application, for the reasonable selection of protective measures, prolonging the using life of equipments and materials and reducing the economic loss caused by corrosion.
In this paper, atmospheric exposure tests were carried out in the desulfurization tower, testing centers of the petrochemical plant and atmospheric corrosion of Wuhan National Field Research Stationt with Q235 carbon steel, copper, aluminum, zinc and 20 species of coating system. Rust and corrosion products were analyzed by SEM and XRD. Weatherability and corrosion resistance of the coating system were studied by means of neutral salt spray accelerated test and aging test in laboratories, besides the electrochemical corrosion behavior of the carbon Q235 steel in thin electrolyte film.
The results show that the corrosion of materials in petrochemical atmosphere is a complex process. The corrosion rate of metal in the desulfurization tower research station was higher than the other two stations. The corrosion of Q235 carbon steel in the desulfurization tower was extremely serious, the corrosion rate reached for the C5 level, compared with C3 level in the other two research stations. The characteristics of coating system were compared between outdoor exposure tests and indoor accelerated tests, the results indicated that sprayed aluminum coating has a excellent corrosion resistance, fluorocarbon coating has a great weathering resistance, and zinc-rich and sprayed aluminum primer system possess good corrosion resistance.
The rust layer of carbon steel in the three research sites had a various shapes, and corrosion products were also different, the growth of which had a certain protective function to the substrate. In the petrochemical plant, the corrosion of carbon steel is not uniform corrosion, as there are some cracks between the rust layer and magnesium substrate. We can see that the surful content in the rust layer is very low through the section of line scans. The surface of carbon steel had massive prosperous undulation pellet in the initial period, with the further occurrence of corrosion, the pellets connected for an entire piece of rust layer. However, the corrosion could not be completely hindered, since there were some cracks in the rust layer.
In the thin film containing chloride ion, sulfate ion and the same concentration mixture of the two ions, the chloride ion did a more enormous implication in the corrosion of carbon steel, compared with sulfate ion. The corrosion rate of the Q235 carbon steel in various densities sodium sulfate solution and thin film thickness were studied, the results indicated that:the corrosion rate decreases with the film thickness increases, and then increases; different concentrations of sodium sulfate solution resulted in a different corrosion rate rules. Under the 7μm liquid film, the corrosion rate decreased with the increasing concentration of sodium sulfate solution. In the remaining test of the thin film's thickness and the bulk solution's concentration, the corrosion rate increased with the concentration increased, and then decreased.
引文
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