准东煤烟气中Na_2SO_4形成的量子化学研究  

Quantum chemical study on formation paths of Na_2SO_4 in flue gas of Zhundong coal

作　　者：康志忠[1] 苏逸峰 高满达 孙保民[1] 王迪 KANG Zhizhong;SU Yifeng;GAO Manda;SUN Baomin;WANG Di(Key Laboratory of Condition Monitoring and Control for Power Plant Equipment,Ministry of Education,North China Electric Power University,Beijing 102206,China)

机构地区：[1]华北电力大学电站设备状态监测与控制教育部重点实验室,北京102206

出　　处：《热力发电》2018年第9期56-62,共7页Thermal Power Generation

基　　金：国家科技支撑计划项目(2015BAA04B02)~~

摘　　要：Na_2SO_4对准东煤锅炉结渣影响较大。为探究准东煤中主要含Na无机物(NaCl和NaOH)气相硫酸盐化生成Na_2SO_4的反应机理,利用Materials Studio的Dmol^3模块,基于密度泛函和过渡态理论,对有气相SO_2或SO_3参与的硫酸盐化过程进行模拟,找到各反应经历的过渡态结构、反应能垒及反应焓变。通过各反应的吉布斯自由能对比分析,找出容易进行的反应路径。分析结论与能量计算一致,验证了过渡态搜索的合理性和正确性。结果表明,有SO_3参与的硫酸盐化反应路径NaCl→NaSO_3Cl→NaHSO_4→Na_2SO_4+HCl是准东煤锅炉烟气中Na_2SO_4的主要形成路径。Sodium sulfate will influence the slagging in boilers firing the Zhundong-coal.In order to explore the reaction mechanism of the sulfation of the main inorganic sodium salts(NaCl and NaOH)in gas phase,a study based on the density functional theory and the transition state theory was performed to simulate the process of the sulfation by Dmol3 module in Materials Studio.The sulfation process involving SO2 and SO3 was simulated to find the structure of each transition state(TS),energy barrier and enthalpy change of each reaction.Moreover,through comparison of the Gibbs free energy among each reaction,the reaction paths which is easy going were find out.The conclusions of the analysis were in accordance with the energy calculation results,which verified the rationality and correctness of the transition state search.The results show that,in the post-flame of Zhundong-coal-fired boiler,the main sulfation path to form sodium sulfate is the following process with SO3 participating in:NaCl→NaSO3Cl→NaHSO4→Na2SO4+HCl.

关 键 词：NA2SO4 准东煤 硫酸盐化 量子化学 反应机理 密度泛函 过渡态 反应路径 

分 类 号：TQ534.2[化学工程—煤化学工程]