Citation: Sai ZHOU, Hu LIU, Peng-fei YU, Mao-bo YUAN, Jing-wen XUE, De-fu CHE. Study on the mechanism of oxidation of nitrogen-containing char by CO2 based on density functional theory[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(1): 19-27. doi: 10.19906/j.cnki.JFCT.2021061 shu

Study on the mechanism of oxidation of nitrogen-containing char by CO2 based on density functional theory

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  • In order to obtain the NO formation mechanism during the coal combustion, the heterogeneous oxidation of nitrogen-containing char by CO2 were investigated based on density functional theory. Simplified char models containing pyrrole nitrogen or pyridine nitrogen were selected as the carbonaceous surfaces. Geometric optimizations were carried out at the B3LYP-D3/6-31G(d) level. Energies of optimized geometries were calculated at the B3LYP-D3/def2-TZVP level. The results show that CO2 oxidation of nitrogen-containing char is composed of three stages: namely CO2 adsorption, CO desorption and NO desorption. In the reaction of CO2 heterogeneous oxidation of pyrrole nitrogen-containing char, CO2 molecules tend to absorb in the C−O−down mode (C−C bonding, N−O bonding) to form a five-membered heterocyclic structure containing nitrogen and oxygen atoms. Then, the surface carbonyl groups and N(O) are formation as the C−O bonds of the original CO2 molecules in the five-membered ring broken to desorb CO and NO, respectively. The reaction is 401.2 kJ/mol endothermic, and the highest energy barrier is 197.6 kJ/mol. In the reaction of CO2 heterogeneous oxidation of pyridine nitrogen-containing char, CO2 molecules tend to form six-membered heterocyclic ring containing nitrogen and oxygen atoms after adsorption in the C−O−down and C−C bonding and C−O bonding mode. And then CO and NO molecules are desorbed. The reaction is 598.6 kJ/mol endothermic, and the energy barrier of rate-determining step is 292.0 kJ/mol.
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