黄磷尾气中有害杂质对锅炉材料影响研究

【作者】 马晓宁；

【导师】 宁平；

【作者基本信息】 昆明理工大学 ， 环境工程， 2008， 硕士

【摘要】 近年来,全球黄磷生产的重心已转移到中国,我国黄磷企业的产能在逐步扩大,因此合理利用黄磷尾气、保护环境成为我国黄磷企业所面临的重大课题。黄磷尾气中富含CO,可作为燃料利用。但因黄磷尾气高温下的强腐蚀性,使黄磷尾气至今未能作为锅炉燃气得到利用。论文就如何将黄磷尾气作为锅炉燃气合理使用进行了初步研究,具体研究内容为:（1）论文对生产过程中产生的实际黄磷尾气,进行了较为全面的分析测试。现场测定了实际黄磷尾气中CO、O、CO₂、总磷、PH₃、H₂S、COS、SO₂、CS₂、As和HF的含量,并查阅相关文献,总结分析了其中一些杂质的单一腐蚀特性。（2）从锅炉材料入手,通过黄磷尾气实际腐蚀失效构件的电镜及能谱分析、腐蚀构件表层剥落物的XPS检测和现场挂片试验,对黄磷尾气高温腐蚀特性进行了初步研究。由对腐蚀失效构件的电镜及能谱分析,可得出构件中P、S含量明显增加,而Fe含量明显减小;通过腐蚀构件表层剥落物的XPS检测,可看出剥落物中均含有磷酸盐或焦磷酸盐和As₂O₃;通过对现场挂片试样的金相与电镜观测,可知被腐蚀后的试样在表面形成了与二元磷共晶与三元磷共晶相似的晶体;通过对现场挂片试样的机械性能测试,可知腐蚀后材料各项机械性能指标均低于腐蚀前。初步估算出PH₃含量应小于24.9mg/Nm³、H₂S量应小于3.3mg/Nm³,才能保证锅炉在使用期时间内正常运行。（3）黄磷尾气的强腐蚀性主要是由于磷及其化合物和硫及其化合物所引起。黄磷尾气燃烧过程中的腐蚀问题,可通过对黄磷尾气中的腐蚀性物质净化脱除来解决。（4）碱洗-催化氧化法是课题组前期研究的成果,论文对该工艺用于燃气的可行性进行了讨论。更多还原

【Abstract】 In recent years, the global yellow phosphorus production center has been transferred to China. The productivity of phosphorus enterprise in China have been enlarged day by day. Rational utilization of yellow phosphorus tail gas and enviroment protection have became an important task. Yellow phosphorus tail gas which contains a lot of CO can be used as fuel. However, because of its strong corrosion behavior in high temperature yellow phosphorus tail gas cannot been utilized as boiler fuel. How to use yellow phosphorus tail gas as boiler fuel has been preliminary studied.（1） Yellow phosphorus tail gas which comes from the process of yellow phosphorus production have been comprehensive analysed and tested. In the papers, CO, O, CO₂, total phosphorus, PH₃, H₂S, COS, SO, CS₂, As and HF in the yellow phosphorus tail gas have been tested at the scene. According to the relevant references, the corrosion behavior of some of them have been summarized and analysed.（2） The corrosion behavior of yellow phosphorus tail gas has been preliminary studied and analysed in the papers through the testing corrosion failure tube by SEM and EDS, corrosion of spalling by XPS and the corrosion test. According to the analysis of the testing corrosion failure tube by SEM and EDS, corrosion of spalling by XPS and the corrosion test can be drawn that the content of P, S is increased but Fe is significantly reduced, binary and ternary eutectic phosphorus was formed on the surface of the sample after the corrosion, the mechanical properties of the sample after the corrosion is reduced. In order to keep boiler normal operation the content of PH₃ and H₂S should be less than 24.9 mg/Nm³ and 3.3 mg/Nm³ which is estimated in the paper.（3） The corroding of yellow phosphorus tail gas is caused by phosphorus, phosphorus compounds, sulfur and sulfur compounds. Removing corrosive substances from yellow phosphorus tail gas is one of the methods to solve the problem of corroding of yellow phosphorus tail gas.（4） The feasibility of using purified yellow phosphorus tail gas by caustic washing and catalytic oxidation process which is achievement of our group as fuel have been discussed in the papers.更多还原