煤中吡啶型氮热解机理的量子化学研究  

QUANTUM CHEMICAL STUDY ON THE PYROLYSIS OF PYRIDINIC NITROGEN FUNCTIONALITIES IN COAL

作　　者：刘海明[1] 张军营[1] 郑楚光[1] 王春梅[1] 

机构地区：[1]煤燃烧国家重点实验室

出　　处：《煤炭转化》2004年第2期19-22,共4页Coal Conversion

基　　金：国家自然科学基金资助项目 ( 4 0 2 72 0 71)

摘　　要：用密度泛函 ( DFT)方法 ,在 UB3LYP/6- 31 G( d)水平上研究了煤中吡啶型氮的热解机理 ,对热解过程中由于官能团周围环境的不同而形成的三类吡啶自由基进行了量子化学计算 ,通过对键的 Mulliken布居数等计算结果的分析 ,分别得到了这三类自由基的热解途径 .并优化得到了反应物、中间体和产物的几何构型 .计算结果表明 ,吡啶型氮主要是以 HCN的形式释放出来的 .NH3 是 HCN二次反应的产物 .The pryolysis mechanisms of pyridinic nitrogen in coal have been investigated using density functional theory(DFT) UB3LYP/6-31G(d) in this paper.Three types of pyridinic free radicals which were produced in the pyrolysis process of pyridinic nitrogen functionalities were studied by quantum chemistry calculation.Comparing the Bond Mulliken population,we found which bond was the initial bond for pyrolysis and then we got the intermediate.Based on our calculation,mechanisms of pyrolysis of pyridinic nitrogen in coal were proposed and discussed.The results show that pyridinic nitrogen is released in the form of HCN,NH 3 is the result from secondary reaction of HCN.

关 键 词：煤 吡啶型氮 热解机理 量子化学 自由基 Mulliken布居数 密度泛函方法 氮氧化物 

分 类 号：TQ530.2[化学工程—煤化学工程] O641.121[理学—物理化学]