摘要
氯气的活化氧化腐蚀是生物质锅炉过热器腐蚀的主要原因之一。为探究活化氧化腐蚀循环中Fe Cl2与O2的反应机理,本文利用Material Studio中的DMOl3模块,基于密度泛函和过渡态理论,优化了各反应物、产物、中间体和过渡态的几何构型。通过频率分析证实了中间体和过渡态的真实性。结果表明,Fe Cl2与O2反应生成Fe3O4的过程中逐次生成3个Cl2分子,其中第三个Cl2逸出生成Fe3O4需要吸收高达300.4 kJ/mol的能量,为反应路径的速率决定步骤。
Activated oxidative corrosion of chlorine is one of the main causes of corrosion in biomass boiler superheaters.To investigate the reaction mechanism of Fe Cl2and O2in the activated oxidation corrosion cycle,the DMOl3module in Material Studio was used to optimize the geometry of each reactant,product,intermediate and transition state based on density functional theory and transition state theory.The authenticity of the intermediates and transition states was confirmed by frequency analysis.The results show that three Cl2molecules are successively formed during the reaction of Fe Cl2with O2to form Fe3O4.The third Cl2 escaping to form Fe3O4 needs to absorb up to 300.4 k J/mol,which is the rate determining step of the reaction pathway.
作者
吕泽康
龙慎伟
李冠兵
牛胜利
路春美
韩奎华
王永征
LYU Zekang;LONG Shenwei;LI Guanbing;NIU Shengli;LU Chunmei;HAN Kuihua;WANG Yongzheng(School of Energy and Power Engineering,Shandong University,Jinan 250061,Shandong,China;Shandong Fengyuan Biomass Power Co.,Ltd.,Zaozhuang 277300,Shandong,China)
出处
《化工学报》
EI
CAS
CSCD
北大核心
2019年第11期4370-4376,共7页
CIESC Journal
基金
国家自然科学基金项目(51576117)
山东省重点研发计划项目(2018GSF117034)
山东大学青年学者未来计划资助项目(2015WLJH33)
关键词
生物质燃料
过热器
CL2
活化氧化
腐蚀
分子模拟
密度泛函理论
biofuel
superheater
chlorine
activated oxidation
corrosion
molecular simulation
density functional theory
