锅炉炉管管材在含SO_4~(2-)和Cl~-介质中的腐蚀研究
摘要
随着机组参数的提高,对锅炉给水品质的要求也越严格。如果给水中杂质离子含量超过允许浓度,将加速炉管的结垢和腐蚀,严重时将导致爆管。本文重点研究了Cl~-和SO_4~(2-)对水冷壁管的点蚀特性,并分析了其腐蚀机理,不仅为制定电站锅炉炉水中Cl~-和SO_4~(2-)的控制标准提供理论依据,确保电厂的安全经济运行;也为水冷壁管在含Cl~-和SO_4~(2-)炉水中的腐蚀特征与防护技术研究奠定了理论基础。
本文针对水冷壁管材20G、15CrMoG和12Cr1MoVG,通过常温电化学实验和高温挂片实验,在含Cl~-和SO_4~(2-)的模拟低磷酸盐-低氢氧化钠水工况溶液中,对三种管材的常温性能和高温腐蚀特性进行分析,用透反射金相显微镜、扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)对试片表面形态和组分进行表征与分析,并对Cl~-和SO_4~(2-)促进或减缓点蚀的机理进行了初步探讨。得出的主要结论如下:
(1)常温下,Cl~-促进未钝化的20G、15CrMoG和12Cr1MoVG电极及其钝化电极的溶解。SO_4~(2-)对未钝化20G电极及其钝化电极的腐蚀有促进作用,但会提高未钝化的15CrMoG和12Cr1MoVG电极及其钝化电极的耐蚀性能。Cl~-/SO_4~(2-)提高未钝化的20G试片及其钝化试片的耐蚀性,降低了未钝化的15CrMoG和12Cr1MoVG试片及其钝化试片的耐蚀性。
(2)高温下条件下,Cl~-对未钝化的20G、15CrMoG和12Cr1MoVG及其钝化试片的侵蚀性严重,促进材料的溶解,加速材料的点蚀。在实际运行中应分别控制Cl~-浓度低于0.2 mg·L~(-1)、0.2 mg·L~(-1)和0.6 mg·L~(-1)。而对于钝化试片,则应分别控制Cl~-浓度低于0.2 mg·L~(-1)、0.4 mg·L~(-1)和0.6 mg·L~(-1)。
(3)高温条件下,SO_4~(2-)为侵蚀性离子,会促进未钝化的20G、15CrMoG和12Cr1MoVG试片及其钝化试片溶解,加速材料的点蚀。在实际运行中,应分别控制溶液中SO_4~(2-)的浓度为0.2 mg·L~(-1),0.6 mg·L~(-1)和1 mg·L~(-1)。对于钝化试片,则应分别控制溶液中的SO42浓度为0.6 mg·L~(-1),1 mg·L~(-1)和1 mg·L~(-1)。
(4)在高温环境中,随着溶液中Cl~-/SO_4~(2-)的增大,未钝化的20G和15CrMoG及其钝化试片的增重速率升高,高温腐蚀速率降低。而对于未钝化的12Cr1MoVG试片及钝化试片,其增重速率升高,高温腐蚀速率先降低后升高。
(5)常温条件下Cl~-促进点蚀的机理是Cl~-与OH-在金属表面发生竞争吸附,形成复合中间体,促进钝化膜的快速溶解。而且SO_4~(2-)和Cl~-在材料表面存在竞争吸附,当Cl~-/SO_4~(2-)较小时,溶液中SO_4~(2-)的含量较高,使得电极表面有效吸附的Cl~-浓度降低,15CrMoG和12Cr1MoVG的耐蚀性增加,而对于20G而言,则是试片表面总的侵蚀性离子含量(Cl~-+SO_4~(2-))增大,试片的侵蚀程度增大。高温条件下Cl~-促进点蚀的机理是由于Cl~-促进Fe2+水解,生成疏松无保护性的Fe3O4,H+浓度增加,局部酸化,点蚀加剧。高温SO_4~(2-)促进点蚀的机理为局部酸化理论,与Cl~-点蚀机理相似。
As the increase of unit parameters, the quality of feed-water require more and more strict. If feed-water contains impurity ions exceeding allowed concentrations, boiler scale and corrosion accelerate, the waterside of water-wall tube corrodes, causing bursting of water-wall tube. Researching the influence of SO_4~(2-) and Cl~- ions on the pitting corrosion of water-wall tube, and analyzing corrosion mechanisms will provide theoretical basis for relevant standards, in order to control SO_4~(2-) and Cl~- ions concentrations in feed-water, and provider theoretical foundation for protection technology, which is valuable on safe and economic operation of power plants.
The purpose of this study is to investigate the influence of Cl~- and SO_4~(2-) ions on the pitting corrosion of water-wall tube 20G, 15CrMoG and 12Cr1MoVG. The effect of Cl~- and SO_4~(2-) ions on pitting corrosion at room temperature and high temperature were assessed by electrochemical and high-temperature weight loss experiments. The specimen surfaces were examined by transmission reflection metallurgical microscopy, scanning electron microscope (SEM), energy disperse spectroscopy (EDS), and X-ray diffraction (XRD). The main conclusions are as follows:
(1) At room temperature, Cl~- accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG. SO_4~(2-) accelerates dissolution of unpassivated and passivated 20G, but enhances corrosion resistance of 15CrMoG and 12Cr1MoVG. Cl~-/SO_4~(2-) enhance corrosion resistance of unpassivated and passivated 20G, but lows corrosion resistance of unpassivated and passivated 15CrMoG and 12Cr1MoVG.
(2) At high temperature, Cl~- accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG. On the unit actual operating condition, Cl~- concentrations must be controlled under 0.2 mg·L~(-1), 0.2 mg·L~(-1) and 0.6 mg·L~(-1) for unpassivated 20G, unpassivated 15CrMoG and unpassivated 12Cr1MoVG, and 0.2 mg·L~(-1), 0.4 mg·L~(-1) and 0.6 mg·L~(-1) for passivated 20G, passivated 15CrMoG and passivated 12Cr1MoVGrespectively.
(3) At high temperature, SO_4~(2-) accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG, and the pitting with jagged edge are formed. On the unit actual operating condition, SO_4~(2-) concentrations must be controlled under 0.2 mg·L~(-1), 0.6 mg·L~(-1) and 1 mg·L~(-1) for unpassivated 20G, unpassivated 15CrMoG and unpassivated 12Cr1MoVG, and 0.6 mg·L~(-1), 1 mg·L~(-1) and 1 mg·L~(-1) for passivated 20G, passivated 15CrMoG and passivated 12Cr1MoVG respectively.
(4) At high temperature, along with Cl~-/ SO_4~(2-) increases, the amount of Cl~- and SO_4~(2-) reduce, mass gain rate of unpassivated and passivated 20G increases, and mass gain rate of unpassivated and passivated 15CrMoG is similar. As Cl~-/ SO_4~(2-) increases, mass gain rate of unpassivated and passivated 12Cr1MoVG increases and then reduces.
(5) At room temperature, pitting corrosion mechanism of Cl~- ions is competition adsorption of Cl~- and OH-, and the adsorbed Cl~- can form an intermediate complex, the passivated film dissolves. Because of competition adsorption of Cl~- and SO_4~(2-), when Cl~-/SO_4~(2-) is low, SO_4~(2-) content is high, the adsorbed Cl~- concentrations reduce, corrosion resistance of 15CrMoG and 12Cr1MoVG enhance. For 20G specimens, the total erosive ions ( Cl~- + SO_4~(2-) ) concentrations increase, specimens dissolve. The corrosion mechanism of Cl~- is proposed to accelerate Fe2+ hydrolysis, and loosely packed Fe3O4 is unprotected, H+ concentrations increase, local acidification can form, pitting corrosion intensifies. The mechanism of SO_4~(2-) ions is the local acidification theory, which is similar to the mechanism of Cl~-.
The result indicated that SO_4~(2-) ions inhibited pit corrosion at room temperature, and accelerated corrosion at high temperature, the critical susceptive SO_4~(2-) ions concentrations was 1 mg·L~(-1).
本文针对水冷壁管材20G、15CrMoG和12Cr1MoVG,通过常温电化学实验和高温挂片实验,在含Cl~-和SO_4~(2-)的模拟低磷酸盐-低氢氧化钠水工况溶液中,对三种管材的常温性能和高温腐蚀特性进行分析,用透反射金相显微镜、扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)对试片表面形态和组分进行表征与分析,并对Cl~-和SO_4~(2-)促进或减缓点蚀的机理进行了初步探讨。得出的主要结论如下:
(1)常温下,Cl~-促进未钝化的20G、15CrMoG和12Cr1MoVG电极及其钝化电极的溶解。SO_4~(2-)对未钝化20G电极及其钝化电极的腐蚀有促进作用,但会提高未钝化的15CrMoG和12Cr1MoVG电极及其钝化电极的耐蚀性能。Cl~-/SO_4~(2-)提高未钝化的20G试片及其钝化试片的耐蚀性,降低了未钝化的15CrMoG和12Cr1MoVG试片及其钝化试片的耐蚀性。
(2)高温下条件下,Cl~-对未钝化的20G、15CrMoG和12Cr1MoVG及其钝化试片的侵蚀性严重,促进材料的溶解,加速材料的点蚀。在实际运行中应分别控制Cl~-浓度低于0.2 mg·L~(-1)、0.2 mg·L~(-1)和0.6 mg·L~(-1)。而对于钝化试片,则应分别控制Cl~-浓度低于0.2 mg·L~(-1)、0.4 mg·L~(-1)和0.6 mg·L~(-1)。
(3)高温条件下,SO_4~(2-)为侵蚀性离子,会促进未钝化的20G、15CrMoG和12Cr1MoVG试片及其钝化试片溶解,加速材料的点蚀。在实际运行中,应分别控制溶液中SO_4~(2-)的浓度为0.2 mg·L~(-1),0.6 mg·L~(-1)和1 mg·L~(-1)。对于钝化试片,则应分别控制溶液中的SO42浓度为0.6 mg·L~(-1),1 mg·L~(-1)和1 mg·L~(-1)。
(4)在高温环境中,随着溶液中Cl~-/SO_4~(2-)的增大,未钝化的20G和15CrMoG及其钝化试片的增重速率升高,高温腐蚀速率降低。而对于未钝化的12Cr1MoVG试片及钝化试片,其增重速率升高,高温腐蚀速率先降低后升高。
(5)常温条件下Cl~-促进点蚀的机理是Cl~-与OH-在金属表面发生竞争吸附,形成复合中间体,促进钝化膜的快速溶解。而且SO_4~(2-)和Cl~-在材料表面存在竞争吸附,当Cl~-/SO_4~(2-)较小时,溶液中SO_4~(2-)的含量较高,使得电极表面有效吸附的Cl~-浓度降低,15CrMoG和12Cr1MoVG的耐蚀性增加,而对于20G而言,则是试片表面总的侵蚀性离子含量(Cl~-+SO_4~(2-))增大,试片的侵蚀程度增大。高温条件下Cl~-促进点蚀的机理是由于Cl~-促进Fe2+水解,生成疏松无保护性的Fe3O4,H+浓度增加,局部酸化,点蚀加剧。高温SO_4~(2-)促进点蚀的机理为局部酸化理论,与Cl~-点蚀机理相似。
As the increase of unit parameters, the quality of feed-water require more and more strict. If feed-water contains impurity ions exceeding allowed concentrations, boiler scale and corrosion accelerate, the waterside of water-wall tube corrodes, causing bursting of water-wall tube. Researching the influence of SO_4~(2-) and Cl~- ions on the pitting corrosion of water-wall tube, and analyzing corrosion mechanisms will provide theoretical basis for relevant standards, in order to control SO_4~(2-) and Cl~- ions concentrations in feed-water, and provider theoretical foundation for protection technology, which is valuable on safe and economic operation of power plants.
The purpose of this study is to investigate the influence of Cl~- and SO_4~(2-) ions on the pitting corrosion of water-wall tube 20G, 15CrMoG and 12Cr1MoVG. The effect of Cl~- and SO_4~(2-) ions on pitting corrosion at room temperature and high temperature were assessed by electrochemical and high-temperature weight loss experiments. The specimen surfaces were examined by transmission reflection metallurgical microscopy, scanning electron microscope (SEM), energy disperse spectroscopy (EDS), and X-ray diffraction (XRD). The main conclusions are as follows:
(1) At room temperature, Cl~- accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG. SO_4~(2-) accelerates dissolution of unpassivated and passivated 20G, but enhances corrosion resistance of 15CrMoG and 12Cr1MoVG. Cl~-/SO_4~(2-) enhance corrosion resistance of unpassivated and passivated 20G, but lows corrosion resistance of unpassivated and passivated 15CrMoG and 12Cr1MoVG.
(2) At high temperature, Cl~- accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG. On the unit actual operating condition, Cl~- concentrations must be controlled under 0.2 mg·L~(-1), 0.2 mg·L~(-1) and 0.6 mg·L~(-1) for unpassivated 20G, unpassivated 15CrMoG and unpassivated 12Cr1MoVG, and 0.2 mg·L~(-1), 0.4 mg·L~(-1) and 0.6 mg·L~(-1) for passivated 20G, passivated 15CrMoG and passivated 12Cr1MoVGrespectively.
(3) At high temperature, SO_4~(2-) accelerates dissolution of unpassivated and passivated 20G, 15CrMoG and 12Cr1MoVG, and the pitting with jagged edge are formed. On the unit actual operating condition, SO_4~(2-) concentrations must be controlled under 0.2 mg·L~(-1), 0.6 mg·L~(-1) and 1 mg·L~(-1) for unpassivated 20G, unpassivated 15CrMoG and unpassivated 12Cr1MoVG, and 0.6 mg·L~(-1), 1 mg·L~(-1) and 1 mg·L~(-1) for passivated 20G, passivated 15CrMoG and passivated 12Cr1MoVG respectively.
(4) At high temperature, along with Cl~-/ SO_4~(2-) increases, the amount of Cl~- and SO_4~(2-) reduce, mass gain rate of unpassivated and passivated 20G increases, and mass gain rate of unpassivated and passivated 15CrMoG is similar. As Cl~-/ SO_4~(2-) increases, mass gain rate of unpassivated and passivated 12Cr1MoVG increases and then reduces.
(5) At room temperature, pitting corrosion mechanism of Cl~- ions is competition adsorption of Cl~- and OH-, and the adsorbed Cl~- can form an intermediate complex, the passivated film dissolves. Because of competition adsorption of Cl~- and SO_4~(2-), when Cl~-/SO_4~(2-) is low, SO_4~(2-) content is high, the adsorbed Cl~- concentrations reduce, corrosion resistance of 15CrMoG and 12Cr1MoVG enhance. For 20G specimens, the total erosive ions ( Cl~- + SO_4~(2-) ) concentrations increase, specimens dissolve. The corrosion mechanism of Cl~- is proposed to accelerate Fe2+ hydrolysis, and loosely packed Fe3O4 is unprotected, H+ concentrations increase, local acidification can form, pitting corrosion intensifies. The mechanism of SO_4~(2-) ions is the local acidification theory, which is similar to the mechanism of Cl~-.
The result indicated that SO_4~(2-) ions inhibited pit corrosion at room temperature, and accelerated corrosion at high temperature, the critical susceptive SO_4~(2-) ions concentrations was 1 mg·L~(-1).
引文
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