对煤制气再燃低NOx燃烧过程进行分析,采用量子化学密度泛函理论(DFT)研究NH2自由基与NO的反应机理.全参数优化了各反应物、中间体、过渡态和产物的几何构型,并计算了它们的能量,通过振动频率分析证实中间体和过渡态的真实性.同时用内禀反应坐标(IRC)计算以进一步确定过渡态.为了得到更精确的能量信息,在QCISD(T)水平上计算了单点能.对NH2自由基与NO反应机理进行分析比较,并通过模拟NH2自由基与NO的反应,得出通道NH2+ NO→ IM1→TS1→IM3→N2+ H2O的活化能最低(206.1kJ/mol),为最佳反应通道.揭示其微观机理,对进一步认识再燃脱氮的本质和主要过程提供了重要的理论依据和实践指导.
参考文献
| [1] | Tree DR.;Clark AW. .Advanced reburning measurements of temperature and species in a pulverized coal flame[J].Fuel,2000(13):1687-1695. |
| [2] | B.J.Zhong;W.W.Shi;W.B.Fu .Effects of fuel characteristics on the NO reduction during the reburning with coals[J].Fuel Processing Technology,2002(2):93-106. |
| [3] | 樊俊杰,张忠孝,金晶.煤粉再燃燃烧含氮组分转化机理的敏感性分析[J].工程热物理学报,2008(12):2145-2148. |
| [4] | 刘栗,邱朋华,吴少华.煤热解挥发分还原NO的反应过程分析[J].工程热物理学报,2010(02):331-334. |
| [5] | Foresman J B;Frisch A.Exploring chemistry with electronic structure methods[M].Pittsburgh:Gaussian,Inc,1996 |
| [6] | Hartmut Spliethoff;Ulrich Greul;Helmut Rudiger et al.Basic effects on NOr emissions in air staging and reburning at a bench-scale test facility[J].Fuel,1996,75(05):560. |
| [7] | Tyrrell J;Kar T;Bartolotti L J .A study of the mechanism of the reaction between 0zone and the chlorine atom using density functional theory[J].Journal of Physical Chemistry A,2001,105(16):4065. |
| [8] | 潘秀梅,王荣顺,苏忠民,James Tyrrell.O（3P）+O2H→OH+O2反应机理的密度泛函理论研究[J].高等学校化学学报,2001(12):2077-2080. |
| [9] | Yao-Yuan Chuang;Elena L. Coitino;Donald G. Truhlar .How Should We Calculate Transition State Geometries for Radical Reactions? The Effect of Spin Contamination on the Prediction of Geometries for OPen-Shell Saddle Points[J].The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory,2000(3):446-450. |
| [10] | Reed A E;Curtiss L A;Weinhold F .Intermolecular interactions from a natural bond orbital,donor-acceptor viewpoint[J].Chemical Reviews,1988,88(06):899. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%