不同Cr含量的奥氏体不锈钢在700℃煤灰/高硫烟气环境中的腐蚀行为

doi:10.11900/0412.1961.2020.00496

金属学报

2022, Vol. 58

Issue (1): 67-74 DOI: 10.11900/0412.1961.2020.00496

研究论文

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不同Cr含量的奥氏体不锈钢在700℃煤灰/高硫烟气环境中的腐蚀行为

曹超¹, 蒋成洋¹(

), 鲁金涛²(

), 陈明辉¹, 耿树江¹, 王福会¹

^1. 东北大学沈阳材料科学国家研究中心东北大学联合研究分部沈阳 110819
^2. 西安热工研究院有限公司电站清洁燃烧国家工程研究中心西安 710032

Corrosion Behavior of Austenitic Stainless Steel with Different Cr Contents in 700^oC Coal Ash/High Sulfur Flue-Gas Environment

CAO Chao¹, JIANG Chengyang¹(

), LU Jintao²(

), CHEN Minghui¹, GENG Shujiang¹, WANG Fuhui¹

^1. Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China
^2. National Energy R&D Center of Clean and High-Efficiency Fossil-Fired Power Generation Technology, Xi'an Thermal Power Research Institute Co. , Ltd. , Xi'an 710032, China

引用本文:

曹超, 蒋成洋, 鲁金涛, 陈明辉, 耿树江, 王福会. 不同Cr含量的奥氏体不锈钢在700℃煤灰/高硫烟气环境中的腐蚀行为[J]. 金属学报, 2022, 58(1): 67-74.
Chao CAO, Chengyang JIANG, Jintao LU, Minghui CHEN, Shujiang GENG, Fuhui WANG. Corrosion Behavior of Austenitic Stainless Steel with Different Cr Contents in 700^oC Coal Ash/High Sulfur Flue-Gas Environment[J]. Acta Metall Sin, 2022, 58(1): 67-74.

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摘要:

研究了3种不同Cr含量(质量分数)的奥氏体不锈钢在700℃下煤灰/高硫烟气环境中的腐蚀行为。结果表明，低Cr合金(19.13%)腐蚀最为严重，氧化膜由外层Fe₂O₃、内层Cr₂O₃及CrS组成，外层氧化膜剥落严重；中Cr合金(22.78%)氧化膜结构与低Cr合金类似，但腐蚀程度更轻；高Cr合金(24.00%)表面形成了稳定而致密的Cr₂O₃层，表现出比其他2种合金更好的抗高温腐蚀性。合金中的NbC会被氧化成Nb₂O₅分布在氧化膜中，Nb₂O₅的形成会破坏氧化膜的完整性，导致氧化膜更容易发生开裂。

关键词 ：高温腐蚀, 奥氏体不锈钢, 煤灰/高硫烟气, 硫化/氧化

Abstract：

With the rapid increase in thermal power generation units in China, the thermal power generation industry is facing pressures such as reducing costs, improving power generation efficiency and mitigating environmental problems. Thermal power generation units with a large capacity and high parameters result in high system efficiency, but they also amplify the corrosion failure problem of high-temperature components, especially the atmosphere/ash corrosion of outer tubes. Many studies regarding flue gas corrosion have shown that molten alkali metal sulfate can form on the surface of pipelines, causing severe corrosion damage, and the extent of corrosion is closely related to the sulfur content in raw coal. However, much attention has been paid to low-sulfur (standard coal combustion) environments in previous studies, with very few studies on high-sulfur environments. Austenitic stainless steels possessing a combination of excellent high temperature corrosion and fatigue resistances, are considered as promising construction materials for high temperature components in supercritical and ultra-supercritical fossil fuel power plants. Elements such as Cr and Nb have been shown to greatly affect the high temperature corrosion resistance of austenitic stainless steels; however few reports are available regarding the effect of Cr on corrosion resistance in high-sulfur flue gas environments and the effect of Nb on the corrosion resistance of Cr₂O₃-forming alloys. Therefore, in this study, the corrosion behavior of three types of austenitic stainless steels with different Cr contents was studied in a coal ash/high-sulfur flue gas environment at 700^oC. Results showed that low Cr alloys formed a two-layered structure: an external Fe₂O₃ layer and an internal layer with Cr₂O₃ and CrS. Medium Cr alloys developed a similar structure oxide scale to low Cr concentration alloys, but the corrosion extent was modest. Conversely, a stable and dense Cr₂O₃ layer was formed on the surface of the high Cr alloys, showing higher corrosion resistance than the other two alloys. The Nb in the alloys had some influence on the corrosion resistance of the alloys. The NbC in the alloys oxidized to Nb₂O₅ and distributed in the oxide scale. The formation of Nb₂O₅ destroyed the integrity of the oxide scale and led to the easy cracking of the oxide scale.

Key words： high temperature corrosion austenitic stainless steel coal-ash/high sulfur flue-gas sulfidation/oxidation

收稿日期: 2020-12-08

ZTFLH:

TG174.44

基金资助:国家重点研发计划项目(2019YFF0217500);辽宁省优秀青年基金项目(2019-YQ-03);中国华能集团有限公司科技项目(HNKJ20-H43)

作者简介: 曹超，男，1994年生，硕士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00496 或 https://www.ams.org.cn/CN/Y2022/V58/I1/67

表1 3种试样的化学成分 (mass fraction / %)

图1 模拟煤灰/烟气腐蚀实验装置示意图

图2 3种样品在700℃下腐蚀1000 h的质量变化曲线

图3 3种样品在700℃下腐蚀1000 h后的XRD谱

图4 3种样品在700℃腐蚀1000 h后的表面形貌

图5 3种样品在700℃腐蚀1000 h后的截面形貌

图6 低Cr合金在700℃腐蚀1000 h后的背散射电子像(BEI)及EPMA面扫结果

图7 中Cr合金在700℃腐蚀1000 h后的BEI及EPMA面扫结果

图8 高Cr合金在700℃腐蚀1000 h后的BEI及EPMA面扫结果

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