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

热解二次反应中煤灰对硫迁移特性的影响机制

贾鑫 王勤辉 张玉辉 韩振南 宋兴飞 王超 付亮亮 许光文

贾鑫, 王勤辉, 张玉辉, 韩振南, 宋兴飞, 王超, 付亮亮, 许光文. 热解二次反应中煤灰对硫迁移特性的影响机制[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2021081
引用本文: 贾鑫, 王勤辉, 张玉辉, 韩振南, 宋兴飞, 王超, 付亮亮, 许光文. 热解二次反应中煤灰对硫迁移特性的影响机制[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2021081
JIA Xin, WANG Qin-hui, ZHANG Yu-hui, HAN Zhen-nan, SONG Xing-fei, WANG Chao, FU Liang-liang, XU Guang-wen. The effects of coal ash on sulfur transformation during secondary reactions of coal pyrolysis[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2021081
Citation: JIA Xin, WANG Qin-hui, ZHANG Yu-hui, HAN Zhen-nan, SONG Xing-fei, WANG Chao, FU Liang-liang, XU Guang-wen. The effects of coal ash on sulfur transformation during secondary reactions of coal pyrolysis[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2021081

热解二次反应中煤灰对硫迁移特性的影响机制

doi: 10.19906/j.cnki.JFCT.2021081
基金项目: 辽宁省教育厅科研项目(LZ2020003)资助
详细信息
    作者简介:

    贾鑫:jiaxin@syuct.edu.cn

    通讯作者:

    Tel: 0510-87952802, E-mail: qhwang@cmee.zju.edu.cn

  • 中图分类号: TQ530.2

The effects of coal ash on sulfur transformation during secondary reactions of coal pyrolysis

Funds: The project was supported by Scientific Research Project of Education Department of Liaoning Province (LZ2020003)
  • 摘要: 煤灰作为热载体的热解二次反应中存在煤灰和挥发分的交互反应,势必影响到热解产物的分布特性。为此,本研究将在固定床反应器上研究二次反应过程中煤灰对硫迁移特性的影响规律。实验结果表明,小龙潭煤灰在二次反应过程中的低温阶段抑制了H2S和COS的析出,主要归因于煤灰中Fe2O3对含硫气体的固定;然而在高温阶段(≥ 800 ℃)促进了H2S和COS的析出,这是由于煤灰中硫酸钙与热解煤气发生还原反应生成了大量的H2S和COS。为进一步揭示煤灰在高温下的作用机制,研究了煤灰主要组分Fe2O3和CaSO4的影响规律,发现800 ℃时添加Fe2O3显著降低了煤气中H2S和COS的析出量,而CaSO4促进了H2S和COS的析出,证明了煤灰对含硫气体的影响规律与其所含的Fe2O3和CaSO4密切相关。
  • 图  1  煤热解燃烧分级转化原理示意图

    Figure  1  Principle of the coal staged conversion process

    图  2  快速升温装置流程图

    Figure  2  Schematic of the experimental apparatus

    图  3  XLT煤灰在二次反应过程中对H2S析出特性的影响

    Figure  3  Effects of XLT ash on H2S release during secondary reactions

    图  4  XLT灰在二次反应过程中对COS析出特性的影响

    Figure  4  Effects of XLT ash on COS release during secondary reactions

    图  5  XLT灰在二次反应过程中对CH3SH析出特性的影响

    Figure  5  Effects of XLT ash on CH3SH release during secondary reactions

    图  6  不同类型的煤灰在二次反应过程中对煤气中含硫组分生成特性的影响

    Figure  6  Effects of ash type on sulfur-containing gases during secondary reactions

    (coal: XLT lignite; ash: XLT-ash, SM-ash; pyrolysis temperature: 800 ℃)

    图  7  煤灰、硫酸钙和三氧化二铁在二次反应过程中对煤气含硫组分生成特性的影响

    Figure  7  Effects of XLT ash, CaSO4 and Fe2O3 on H2S during secondary reactions

    (coal:XLT lignite; ash: XLT-ash; pyrolysis temperature:800 ℃)

    图  8  XLT灰在二次反应过程中对焦油中硫含量的影响规律

    Figure  8  Effects of XLT ash on tar sulfur during secondary reactions

    表  1  煤质分析

    Table  1  Main characteristics of XLT coal

    SampleProximate analysis wd/% Ultimate analysis wd/% Sulfur Forms analysis wd/%
    MVACHNO*StSsSpSo*
    XLT4.8039.6119.36 54.383.721.1518.272.28 0.050.571.66
    SHM2.9326.8120.7659.633.450.8214.430.680.020.390.27
    M: moisture; V: volatile, A: ash; St: total sulfur; Sp: pyritic sulfur; Ss: sulfate sulfur; So: organic sulfur, O*, So*: by difference; O* = 100−MA−C−H−N−S, So* = St−Ss−Sp
    下载: 导出CSV

    表  2  煤灰成分分析

    Table  2  Analysis of ash compositions in raw coals

    SampleComposition w/%
    SiO2Fe2O3Al2O3CaOMgOK2ONa2OSO3othersa
    XLT22.7911.689.7123.154.050.660.1327.122.94
    SHM33.765.4547.276.460.950.320.154.071.57
    a: by difference
    下载: 导出CSV

    表  3  煤灰中CaSO4在二次反应过程的分解率

    Table  3  CaSO4 decomposition rate during secondary reactions

    600 ℃800 ℃Blank sample
    Decomposition rate/%0.947.20.4
    备注:空白试验与正常试验区别为:正常试验前半部分放置煤,后半部分放置煤灰;空白试验前半部分不放置任何物质,后半部分放置煤灰。
    下载: 导出CSV
  • [1] QU X, LIANG P, ZHANG R, GAN Z, BI J. Sulfur transformation in the process of circulating fluidized bed combustion combined with coal pyrolysis[J]. Energy Fuels,2010,24(9):5023−5027.
    [2] QU X, LIANG P, WANG Z, ZHANG R, SUN D, GONG X, GAN Z, BI J. Pilot development of polygonation process of circulating fluidized bed combustion combined with coal pyrolysis[J]. Chem Eng Technol,2011,34(1):61−68.
    [3] XIONG R, DONG L, YU J, ZHANG X, JIN L, XU G. Fundamentals of coal topping gasification: Characterization of pyrolysis topping in a fluidized bed reactor[J]. Fuel Process Technol,2010,91(8):810−817. doi: 10.1016/j.fuproc.2009.07.005
    [4] CHEN Y, HE R. Fragmentation and diffusion model for coal pyrolysis[J]. J Anal Appl Pyrolysis,2011,90(1):72−79. doi: 10.1016/j.jaap.2010.10.007
    [5] HONG D, CAO Z, GUO X. Effect of calcium on the secondary reactions of tar from Zhundong coal pyrolysis: A molecular dynamics simulation using ReaxFF[J]. J Analy Appl Pyrolysis,2019,137:246−252. doi: 10.1016/j.jaap.2018.11.033
    [6] TSUBOUCHI N, OHTSUKA Y. Nitrogen chemistry in coal pyrolysis: Catalytic roles of metal cations in secondary reactions of volatile nitrogen and char nitrogen[J]. Fuel Process Technol,2008,89(4):379−390. doi: 10.1016/j.fuproc.2007.11.011
    [7] XU W C, TOMITA A. The effects of temperature and residence time on the secondary reactions of volatiles from coal pyrolysis[J]. Fuel Process Technol,1989,21(1):25−37. doi: 10.1016/0378-3820(89)90012-X
    [8] ZHANG H, FLETCHER T H. Nitrogen transformations during secondary coal pyrolysis[J]. Energy Fuels,2001,15(6):1512−1522.
    [9] ZHANG Y Q, PAN D F, QU X, LIANG P. Secondary catalytic effect of circulating ash on the primary volatiles from slow and fast pyrolysis of coal[J]. Energy Fuels,2018,32(2):1328−1335.
    [10] LIN Y H, CHEN Y C, CHU H. The mechanism of coal gas desulfurization by iron oxide sorbents[J]. Chemosphere,2015,121:62−67. doi: 10.1016/j.chemosphere.2014.11.010
    [11] 沈洪波, 张辉, 刘应书, 李皓琰, 张贺, 郝智天. 改性Fe2O3脱硫剂脱除H2S反应特性[J]. 环境工程学报,2015,9(9):4458−4464. doi: 10.12030/j.cjee.20150958

    SHEN Hong-bo, ZHANG Hui, LIU Ying-shu, LI Hao-yan, ZHANG He, HAO Zhi-tian. Reaction characteristics of removal of H2S by modified Fe2O3 desulfurizer[J]. Chin J Environ Eng,2015,9(9):4458−4464. doi: 10.12030/j.cjee.20150958
    [12] 宋华, 罗威, 许林祥, 张娇静. Al2O3/Fe2O3吸附剂脱除硫化氢的性能[J]. 化工进展,2013,32(4):779−785.

    SONG Hua, LUO Wei, XU Lin-xiang, ZHANG Jiao-jing. Performance of Al2O3/Fe2O3 in H2S adsorption[J]. Chem Ind Eng Prog,2013,32(4):779−785.
    [13] 王娜, 马国明. 活性Fe2O3脱硫剂脱除页岩干馏瓦斯气中H2S的能力分析[J]. 露天采矿技术,2008,(z1):86−87. doi: 10.3969/j.issn.1671-9816.2008.z1.041

    WANG Na, MA Guo-ming. Ability analysis of active Fe2O3 desulfurizer to remove H2S from gas in shale retorting[J]. Opencst Min Technol,2008,(z1):86−87. doi: 10.3969/j.issn.1671-9816.2008.z1.041
    [14] XIAO R, SONG Q. Characterization and kinetics of reduction of CaSO4 with carbon monoxide for chemical-looping combustion[J]. Combust Flame,2011,158(12):2524−2539. doi: 10.1016/j.combustflame.2011.05.011
    [15] TIAN H, GUO Q, YUE X, LIU Y. Investigation into sulfur release in reductive decomposition of calcium sulfate oxygen carrier by hydrogen and carbon monoxide[J]. Fuel Process Technol,2010,91(11):1640−1649. doi: 10.1016/j.fuproc.2010.06.013
    [16] WANG M, HU Y, WANG J, CHANG L, WANG H. Transformation of sulfur during pyrolysis of inertinite-rich coals and correlation with their characteristics[J]. J Analy Appl Pyrolysis,2013,104:585−592. doi: 10.1016/j.jaap.2013.05.010
    [17] ZHOU Q, HU H Q, LIU Q R, ZHU S W, ZHAO R. Effect of atmosphere on evolution of sulfur-containing gases during coal pyrolysis[J]. Energy Fuels,2005,19(3):892−897. doi: 10.1021/ef049773p
    [18] 周强. 煤的热解行为及硫的脱除[D]. 大连: 大连理工大学, 2004.

    ZHOU Qiang. Behavior of coal and sulfur removal during pyrolysis[D]. Dalian: Dalian University of Technology, 2004.
    [19] 刘全润. 煤的热解转化和脱硫研究[D]. 大连: 大连理工大学, 2006.

    LIU Quan-run. Coal conversion and desulfurization during pyrolysis[D]. Dalian: Dalian University of Technology, 2004.
    [20] 陈皓侃. 热解和加氢热解过程中硫变迁规律的研究[D]. 太原: 中国科学院山西煤炭化学研究所, 1998.

    CHEN Hao-kan. Sulfur changes during pyrolysis and hydropyrolysis[D]. Taiyuan: Institute of coal chemistry, Chinese Academy of Sciences, 1998.
  • 加载中
图(8) / 表(3)
计量
  • 文章访问数:  11
  • HTML全文浏览量:  5
  • PDF下载量:  4
  • 被引次数: 0
出版历程
  • 收稿日期:  2021-04-19
  • 修回日期:  2021-09-03
  • 网络出版日期:  2021-10-03

目录

    /

    返回文章
    返回