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焦油模型化合物与铁基氧载体的反应特性研究

胡东海 曹国强 杜梅杰 黄戒介 赵建涛 李春玉 房倚天

胡东海, 曹国强, 杜梅杰, 黄戒介, 赵建涛, 李春玉, 房倚天. 焦油模型化合物与铁基氧载体的反应特性研究[J]. 燃料化学学报(中英文), 2023, 51(12): 1739-1750. doi: 10.19906/j.cnki.JFCT.2023037
引用本文: 胡东海, 曹国强, 杜梅杰, 黄戒介, 赵建涛, 李春玉, 房倚天. 焦油模型化合物与铁基氧载体的反应特性研究[J]. 燃料化学学报(中英文), 2023, 51(12): 1739-1750. doi: 10.19906/j.cnki.JFCT.2023037
HU Dong-hai, CAO Guo-qiang, DU Mei-jie, HUANG Jie-jie, ZHAO Jian-tao, LI Chun-yu, FANG Yi-tian. Study on the reaction characteristics of tar model compounds with an Fe-based oxygen carrier[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1739-1750. doi: 10.19906/j.cnki.JFCT.2023037
Citation: HU Dong-hai, CAO Guo-qiang, DU Mei-jie, HUANG Jie-jie, ZHAO Jian-tao, LI Chun-yu, FANG Yi-tian. Study on the reaction characteristics of tar model compounds with an Fe-based oxygen carrier[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1739-1750. doi: 10.19906/j.cnki.JFCT.2023037

焦油模型化合物与铁基氧载体的反应特性研究

doi: 10.19906/j.cnki.JFCT.2023037
基金项目: 中国科学院战略重点研究计划(XDA29050600)资助
详细信息
    通讯作者:

    E-mail: licy@sxicc.ac.cn

  • 中图分类号: TK6

Study on the reaction characteristics of tar model compounds with an Fe-based oxygen carrier

Funds: The project was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA29050600).
  • 摘要: 本研究以生物质/煤的焦油模型化合物(TMCs)为研究对象,在两阶段固定床实验上探究了铁基氧载体(70%Fe2O3/30%Al2O3)对TMCs的转化特性,考察了不同TMCs的反应性及其转化的影响因素。研究发现,TMCs与氧载体的反应活性为:苯酚>蒽>萘,且苯酚转化生成积炭的比例最多(64%),而萘转化生成积炭的比例最少(40%);氧载体与萘的反应程度相对较高,但容易导致氧载体的烧结。此外,积炭表征显示萘生成的积炭在三种TMCs中具有最高的稳定性。增加氧载体的用量和提高反应温度不仅有利于萘和蒽的进一步转化,而且能够增加气相产物中CO2的分率。由于苯酚分子具有较高的反应活性及较强的裂解效果导致其转化率随氧载体用量和反应温度的增加变化较小,然而,较高的反应温度(1000 ℃)导致焦油发生严重的裂解现象并产生大量积炭。三次循环实验结果表明与萘反应的氧载体失活最为严重。
  • FIG. 2801.  FIG. 2801.

    FIG. 2801.  FIG. 2801.

    图  1  实验装置示意图

    Figure  1  Schematic of the experimental set-up

    图  2  不同TMCs的转化率及产物分布

    Figure  2  Conversion and product distribution of different TCMs (t=800 ℃,φ=0.75)

    图  3  与相关TMCs反应后氧载体的XRD谱图

    Figure  3  XRD diagram of oxygen carrier after reaction with relevant TMCs (t=800 ℃, φ=0.75)

    图  4  与相关TMCs反应前后氧载体的SEM照片

    Figure  4  SEM images of the oxygen carrier before and after reaction with relevant TMCs: (a) Fresh oxygen carriers; (b) Reacted with phenol; (c) Reacted with naphthalene; (d) Reacted with anthracene

    图  5  与不同TMCs反应后氧载体的拉曼光谱谱图

    Figure  5  Raman spectra of oxygen carrier reacted with different TMCs

    图  6  与不同TMCs反应后氧载体的(a)升温曲线和(b)失重速率

    Figure  6  Temperature ramping curve (a) and weight loss rate (b) of oxygen carrier after reaction with different TMCs

    图  7  不同反应条件下TCM的转化率

    Figure  7  TMCs conversion under different reaction conditions

    图  8  不同反应条件下TCMs的产物分布

    Figure  8  Product distribution of TCMs under different reaction conditions: (a) Phenol; (b) Naphthalene; (c) Anthracene

    图  9  不同反应条件下晶格氧的利用率

    Figure  9  Utilization rate of lattice oxygen under different reaction conditions

    图  10  不同循环次数下相关TMCs的转化率和产物分布

    Figure  10  Conversion and product distribution of related TMCs for different cycle times (t=900 ℃, φ=1.5)

    表  1  在两阶段固定床反应器中进行的实验操作参数

    Table  1  Summary of experimental operating parameters carried out in the 2-stage fixed bed reactor

    Operating condition1st stage2st stage
    FeedstockTMCsOC: 70% Fe2O3/30% Al2O3
    (0.3−0.8 mm)
    Temperature /℃200800, 900, 1000
    Oxygen/carbon ratio (φ)φ= 0.75, 1.5
    (Corresponding weight of OC = 1.25, 2.5 g)
    (Corresponding bed height of OC = 0.25, 0.5 cm)
    Superficial velocity
    Weight hourly space velocity (WHSV)
    0.007 m/s
    0.047–0.093 h−1
    下载: 导出CSV

    表  2  与相关TMCs反应前后氧载体的比表面积及孔分布

    Table  2  Specific surface area and pore distribution of oxygen carriers before and after reaction with relevant TMCs

    SampleSpecific surface area
    /(m2·g−1)
    Total pore volume
    /(cm3·g−1)
    Pore size distribution
    micropore
    (<2 nm,%)
    mesopore
    (2–50 nm,%)
    macropore
    (>50 nm,%)
    Fresh oxygen carrier11.30.0620.7574.7124.54
    Reacted with phenol12.50.0551.3475.3823.28
    Reacted with naphthalene9.70.0500.6575.2824.07
    Reacted with anthracene10.40.0580.7073.8625.44
    下载: 导出CSV

    表  3  热重实验前后氧载体样品中碳的定量分析

    Table  3  Quantitative analysis of carbon in oxygen carrier before and after thermogravimetric test

    Phenol w/%Naphthalene w/%Anthracene w/%
    Before reaction2.370.791.89
    After reaction0.370.220.29
    下载: 导出CSV

    表  4  TMCs在不同反应条件下的焦油产物

    Table  4  Tar products of TMCs under different reaction conditions

    TMCsReaction productsPeak area of various tar component ( × 106
    φ = 0.75 (t=800 ℃)φ = 1.5 (t=800 ℃)φ = 1.5 (t=900 ℃)φ = 1.5 (t=1000 ℃)
    Phenolbenzene14.45.010.230.11
    toluene0.150.09
    styrene0.140.10
    naphthalene2.952.481.23
    Naphthalenebenzene7.797.763.310.26
    toluene0.150.09
    styrene0.210.45
    naphthalene2582241210.03
    1,1'-binaphthalene3.335.583.34
    Anthracenebenzene3.083.964.65
    toluene0.170.640.93
    styrene0.120.410.52
    naphthalene2.973.674.21
    anthracene67.746.517.4
    下载: 导出CSV
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  • 收稿日期:  2023-03-16
  • 修回日期:  2023-04-10
  • 录用日期:  2023-04-19
  • 网络出版日期:  2023-05-06
  • 刊出日期:  2023-12-05

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