留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

基于密度泛函理论的CO2氧化含氮焦炭的机理研究

周赛 刘虎 于鹏飞 袁茂博 薛景文 车得福

周赛, 刘虎, 于鹏飞, 袁茂博, 薛景文, 车得福. 基于密度泛函理论的CO2氧化含氮焦炭的机理研究[J]. 燃料化学学报(中英文), 2022, 50(1): 19-27. doi: 10.19906/j.cnki.JFCT.2021061
引用本文: 周赛, 刘虎, 于鹏飞, 袁茂博, 薛景文, 车得福. 基于密度泛函理论的CO2氧化含氮焦炭的机理研究[J]. 燃料化学学报(中英文), 2022, 50(1): 19-27. doi: 10.19906/j.cnki.JFCT.2021061
ZHOU Sai, LIU Hu, YU Peng-fei, YUAN Mao-bo, XUE Jing-wen, CHE De-fu. 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
Citation: ZHOU Sai, LIU Hu, YU Peng-fei, YUAN Mao-bo, XUE Jing-wen, CHE De-fu. 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

基于密度泛函理论的CO2氧化含氮焦炭的机理研究

doi: 10.19906/j.cnki.JFCT.2021061
基金项目: 中国博士后科学基金(2018M633507)和陕西省自然科学基础研究计划(2020JQ-063)资助
详细信息
    通讯作者:

    Tel:15389251896,E-mail:epeliuhu@mail.xjtu.edu.cn

  • 中图分类号: TQ534.9

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

Funds: The project was supported by the Postdoctoral Research Foundation of China (2018M633507) and Natural Science Basic Research Plan in Shaanxi Province of China (2020JQ-063)
  • 摘要: 本研究基于密度泛函理论,选取简化的含吡咯氮(N-5)或吡啶氮(N-6)焦炭模型,在分子水平上对CO2氧化含氮焦炭的异相反应机理进行研究。结构优化采用B3LYP-D3/6-31G(d)方法,单点能计算采用B3LYP-D3/def2-TZVP方法。计算结果表明,CO2氧化含氮焦炭过程分为CO2吸附、CO脱附和NO脱附三个阶段。CO2异相氧化含吡咯氮焦炭的反应中,CO2分子倾向于以C−O−down模式(N−O结合、C−C结合)吸附形成含氮和氧的五元杂环结构。然后五元环中原CO2分子的C−O键断裂形成表面羰基和表面氮氧结构,分别解吸附出CO和NO。该反应吸热401.2 kJ/mol,决速步能垒为197.6 kJ/mol。CO2异相氧化含吡啶氮焦炭的反应中,CO2分子以C−O−down和C−C结合、C−O结合模式吸附后倾向于先形成含氮和氧的六元杂环,再发生CO和NO分子的脱附。该反应吸收598.6 kJ/mol的热量,决速步能垒为292.0 kJ/mol。
  • FIG. 1233.  FIG. 1233.

    FIG. 1233.  FIG. 1233.

    图  1  含氮焦炭模型

    Figure  1  Nitrogen-containing char models

    图  2  CO2在含N-5焦炭表面吸附的各驻点结构

    Figure  2  Structures of stagnation points of CO2 adsorption on the surface of pyrrole nitrogen-containing char

    图  3  CO2在含N-5焦炭表面吸附的能量变化

    Figure  3  Potential energy surface of CO2 adsorption on the surface of pyrrole nitrogen-containing char

    图  4  路径a反应过程的各驻点结构

    Figure  4  Structures of stagnation points of path-a

    图  5  路径a反应过程的能量变化

    Figure  5  Potential energy surface of path-a

    图  6  CO2在含N-6焦炭表面的吸附构型与能量变化

    Figure  6  Adsorption configuration and energy of CO2 on the surface of pyridine nitrogen-containing char

    图  7  路径c和路径d反应过程的各驻点结构

    Figure  7  Structures of stagnation points of path-c and path-d

    图  8  路径c反应过程的能量变化

    Figure  8  Potential energy surface of path-c

    图  9  路径d反应过程的能量变化

    Figure  9  Potential energy surface of path-d

    图  10  经典过渡态理论得到的反应速率常数

    Figure  10  Rate constant k calculated from cTST

    表  1  拟合所得动力学反应参数

    Table  1  Fitted kinetic parameters of Arrhenius expressions

    ReactionA /s−1Ea /(kJ·mol−1)
    a-IM1→a-IM27.82 × 1010186.0
    c-IM1→c-IM24.57 × 1013240.2
    IM6→P2+NO3.59 × 1015305.7
    d-IM2→d-IM35.49 × 1012598.2
    下载: 导出CSV
  • [1] 国家统计局. 中国统计年鉴2020[J]. 北京: 中国统计出版社, 2020.

    National Bureau of Statistics of China. China Statistical Yearbook[J]. Beijing: China Statistics Press, 2020.
    [2] 毛洪钧, 李悦宁, 林应超, 王婷, 李维尊, 鞠美庭, 朱复东. 生物质锅炉氮氧化物排放控制技术研究进展[J]. 工程科学学报,2019,41(1):4−14.

    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] 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] 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] 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] 车得福. 煤氮热变迁与氮氧化物生成[M]. 西安: 西安交通大学出版社, 2013.

    CHE De-fu. Thermal Coal-N Transformation and Nitrogen oxide Generation[M]. Xi'an: Xi'an Jiaotong University Press, 2013.
    [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] 张秀霞, 周志军, 周俊虎, 刘建忠, 岑可法. O2氧化含氮焦炭释放CO和NO的量子化学研究[J]. 煤炭学报,2011,36(1):129−134.

    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] 张秀霞. 焦炭燃烧过程中氮转化机理与低NOx燃烧技术的开发[D]. 杭州: 浙江大学, 2012.

    ZHANG Xiu-xia. Nitrogen conversion mechanism during char combustion and develepment of low NOx technology[D]. Hangzhou: Zhejiang University, 2012.
    [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 NOx 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] SALZMANN R, NUSSBAUMER T. Fuel staging for NOx reduction in biomass combustion: experiments and modeling[J]. Energy Fuels, 15(3): 575–582.
    [12] 张泰, 柳朝晖, 黄晓宏, 陈松涛, 王勇, 皮里刚, 郑楚光. 3 MWth富氧燃烧气体污染物生成与排放特性研究[J]. 工程热物理学报,2014,35(8):1652−1655.

    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 MWth oxy-fuel pilot test facility[J]. J Eng Therm,2014,35(8):1652−1655.
    [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] 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] 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] 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] 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] 刘艳华, 车得福, 李荫堂, 惠世恩, 徐通模. X射线光电子能谱确定铜川煤及其焦中氮的形态[J]. 西安交通大学学报,2001,35(7):661−665. doi: 10.3321/j.issn:0253-987X.2001.07.001

    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] 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] 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] 刘烨鸣. 高浓度CO2燃烧条件下NOx转化机理的研究[D]. 扬州: 扬州大学, 2018.

    LIU Ye-ming. Study on NOx conversion mechanism under O2/CO2 combustion with high concentration of CO2[D]. Yangzhou: Yangzhou University, 2018.
    [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] 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] 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] 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] 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] 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] 钟俊, 高正阳, 丁艺, 余岳溪, 杨维结. Zigzag煤焦表面异相还原N2O反应[J]. 煤炭学报,2017,42(11):3028−3034.

    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] 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] FRISCH M J, TRUCKS G W, SCHLEGEL H B, SCUSERIA G E. Gaussian 09 Rev. D. 01[M]. Wallingford, CT. 2009.
    [31] 傅献彩. 物理化学[M]. 5版. 北京: 高等教育出版社, 2005.

    FU Xian-cai. Physical Chemistry[M]. 5th ed. Beijing: Higher Education Press, 2005.
    [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] 田向红. 焦炭氧化的密度泛函理论研究[D]. 郑州: 郑州大学, 2019.

    TIAN Xiang-hong. Study on coke oxidation with density functional theory[D]. Zhengzhou: Zhengzhou University, 2019.
  • 加载中
图(11) / 表(1)
计量
  • 文章访问数:  398
  • HTML全文浏览量:  152
  • PDF下载量:  50
  • 被引次数: 0
出版历程
  • 收稿日期:  2021-04-14
  • 修回日期:  2021-06-03
  • 网络出版日期:  2021-06-25
  • 刊出日期:  2022-01-25

目录

    /

    返回文章
    返回