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

State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

Corresponding author: Hu LIU, epeliuhu@mail.xjtu.edu.cn
Received Date: 14 April 2021
Revised Date: 3 June 2021

Figures(11)

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.
- CO₂,
- nitrogen-containing char,
- heterogeneous oxidation,
- CO,
- NO,
- density functional theory
1. [1]
  National Bureau of Statistics of China. China Statistical Yearbook[J]. Beijing: China Statistics Press, 2020.
2. [2]
  MAO Hong-jun, LI Yue-ning, LIN Ying-chao, WANG Ting, LI Wei-zun, JU Mei-ting, ZHU Fu-dong. Overview of advances in emission control technologies for nitric oxides from biomass boilers[J]. Chin J Eng,2019,41(1):4−14.
3. [3]
  DE SOETE G G, CROISET E, RICHARD J R. Heterogeneous formation of nitrous oxide from char-bound nitrogen[J]. Combust Flame,1999,117(1):140−154.
4. [4]
  MILLER J A, BOWMAN C T. Mechanism and modeling of nitrogen chemistry in combustion[J]. Prog Energy Combust Sci,1989,15(4):287−338. doi: 10.1016/0360-1285(89)90017-8
5. [5]
  WINTER F, WARTHA C, LÖFFLER G, HOFBAUER H. The NO and N₂O formation mechanism during devolatilization and char combustion under fluidized-bed conditions[J]. Symp (Int) Combust,1996,26(2):3325−3334. doi: 10.1016/S0082-0784(96)80180-9
6. [6]
  CHE De-fu. Thermal Coal-N Transformation and Nitrogen oxide Generation[M]. Xi'an: Xi'an Jiaotong University Press, 2013.
7. [7]
  GLARBORG P, JENSEN A D, JOHNSSON J E. Fuel nitrogen conversion in solid fuel fired systems[J]. Prog Energy Combust Sci,2003,29(2):89−113. doi: 10.1016/S0360-1285(02)00031-X
8. [8]
  ZHANG Xiu-xia, ZHOU Zhi-jun, ZHOU Jun-hu, LIU Jian-zhong, CEN Ke-fa. A quantum chemistry study of CO and NO desorption from oxidation of nitrogen-containing char by oxygen[J]. J China Coal Soc,2011,36(1):129−134.
9. [9]
  ZHANG Xiu-xia. Nitrogen conversion mechanism during char combustion and develepment of low NO_x technology[D]. Hangzhou: Zhejiang University, 2012.
10. [10]
  WANG X B, HU Z F, DENG S H, XIONG Y Y, TAN H Z. Effect of biomass/coal co-firing and air staging on NO_x emission and combustion efficiency in a drop tube furnace[J]. Energy Procedia,2014,61:2331−2334. doi: 10.1016/j.egypro.2014.11.1196
11. [11]
  SALZMANN R, NUSSBAUMER T. Fuel staging for NO_x reduction in biomass combustion: experiments and modeling[J]. Energy Fuels, 15(3): 575–582.
12. [12]
  ZHANG Tai, LIU Zhao-hui, HUANG Xiao-hong, CHEN Song-tao, WANG Yong, PI Li-gang, ZHENG Chu-guang. Experimental study of gaseous pollutant formation and emission on 3 MW_th oxy-fuel pilot test facility[J]. J Eng Therm,2014,35(8):1652−1655.
13. [13]
  OHTSUKA Y, WU Z. Nitrogen release during fixed-bed gasification of several coals with CO₂: Factors controlling formation of N₂[J]. Fuel,1999,78(5):521−527. doi: 10.1016/S0016-2361(98)00187-2
14. [14]
  PARK D–C, DAY S J, NELSON P F. Nitrogen release during reaction of coal char with O₂, CO₂, and H₂O[J]. Proc Combust Ins,2005,30(2):2169−2175. doi: 10.1016/j.proci.2004.08.051
15. [15]
  ZHANG H, JIANG X M, LIU J X. Updated effect of carbon monoxide on the interaction between NO and char bound nitrogen: A combined thermodynamic and kinetic study[J]. Combust Flame,2020,220:107−118. doi: 10.1016/j.combustflame.2020.06.032
16. [16]
  ZHANG H, LIU J X, LIU J G, LUO L, JIANG X M. DFT study on the alternative NH₃ formation path and its functional group effect[J]. Fuel,2018,214(FEB):108−114.
17. [17]
  ZHANG H, LIU J X, WANG X Y, LUO L, JIANG X M. DFT study on the C(N)-NO reaction with isolated and contiguous active sites[J]. Fuel,2017,203(SEP):715−724.
18. [18]
  LIU Yan-hua, CHE De-fu, LI Yin-tang, HUI Shi-en, XU Tong-mo. X-Ray photoelectron spectroscopy determination of the forms of nitrogen in Tongchuan coal and its chars[J]. J Xi'an Jiaotong Univ,2001,35(7):661−665. doi: 10.3321/j.issn:0253-987X.2001.07.001
19. [19]
  ZHAO S H, SUN R Y, BI X L, PAN X J, SU Y. Density functional theory study of the heterogenous interaction between char-bound nitrogen and CO₂ during oxy-fuel coal combustion[J]. Combust Flame,2020,216:136−145. doi: 10.1016/j.combustflame.2020.02.026
20. [20]
  CHEN N, YANG R T. Ab initio molecular orbital calculation on graphite Selection of molecular system and model chemistry[J]. Carbon,1998,36(7−8):1061−1070. doi: 10.1016/S0008-6223(98)00078-5
21. [21]
  LIU Ye-ming. Study on NO_x conversion mechanism under O₂/CO₂ combustion with high concentration of CO₂[D]. Yangzhou: Yangzhou University, 2018.
22. [22]
  STEPHENS P J, DEVLIN F J, CHABALOWSKI C F, FRISCH M J. Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields[J]. J Phys Chem,1994,98(45):11623−11627. doi: 10.1021/j100096a001
23. [23]
  SENDT K, HAYNES B S. Density functional study of the chemisorption of O₂ on the zigzag surface of graphite[J]. Combust Flame,2005,143(4):629−643. doi: 10.1016/j.combustflame.2005.08.026
24. [24]
  ZHU Z H, FINNERTY J, LU G Q, YANG R T. A comparative study of carbon gasification with O₂ and CO₂ by density functional theory calculations[J]. Energy Fuels,2002,16(6):1359−1368. doi: 10.1021/ef0200020
25. [25]
  ZHANG H, JIANG X M, LIU J X, SHEN J. Application of density functional theory to the nitric oxide heterogeneous reduction mechanism in the presence of hydroxyl and carbonyl groups[J]. Energy Convers Manage,2014,83(JUL):167−176.
26. [26]
  MONTOYA A, TRUONG T N, SAROFIM A F. Application of density functional theory to the study of the reaction of NO with char–bound nitrogen during combustion[J]. J Phys Chem A,2000,104(36):8409−8417. doi: 10.1021/jp001045p
27. [27]
  STEFAN G. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J]. J Chem Phys,2010,15(132):1−19.
28. [28]
  ZHONG Jun, GAO Zheng-yang, DING Yi, YU Yue-xi, YANG Wei-jie. Heterogeneous reduction reaction of N₂O by char based on zigzag carbonaceous model[J]. J China Coal Soc,2017,42(11):3028−3034.
29. [29]
  GONZALEZ C, SCHLEGEL H B. Reaction path following in mass-weighted internal coordinates[J]. J Phys Chem,1990,94(14):5523−5527. doi: 10.1021/j100377a021
30. [30]
  FRISCH M J, TRUCKS G W, SCHLEGEL H B, SCUSERIA G E. Gaussian 09 Rev. D. 01[M]. Wallingford, CT. 2009.
31. [31]
  FU Xian-cai. Physical Chemistry[M]. 5th ed. Beijing: Higher Education Press, 2005.
32. [32]
  CHEN P, GU M Y, CHEN G, LIU F S, LIN Y Y. DFT study on the reaction mechanism of N₂O reduction with CO catalyzed by char[J]. Fuel,2019,192(9):1682−706.
33. [33]
  TIAN Xiang-hong. Study on coke oxidation with density functional theory[D]. Zhengzhou: Zhengzhou University, 2019.
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Study on the mechanism of oxidation of nitrogen-containing char by CO2 based on density functional theory

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