化学链燃烧过程中铁基烧结返矿载氧体反应活性及结构研究

刘浪; 刘清才; 孟飞; 杨剑; 孔明; 赵冬; 朱博洪; 任山

化学链燃烧过程中铁基烧结返矿载氧体反应活性及结构研究

刘浪^{1, 2},
刘清才^2, ,,
孟飞²,
杨剑²,
孔明²,
赵冬²,
朱博洪²,
任山²

1.
贵州理工学院化学工程学院, 云南贵州 550003
2.
重庆大学材料科学与工程学院, 重庆 400044

基金项目:

重庆市应用开发计划项目 cstc2014yykfB100007

详细信息

中图分类号: TK546
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- 被引次数: 0
出版历程
- 收稿日期: 2016-03-31
- 修回日期: 2016-07-04
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-10-10

Reaction activity and structural characterizations of sintered return fine oxyen carriers in chemical-looping combustion

1.
School of Chemical Engineering, Guizhou Institue of Technology, Guizhou 550003, China
2.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China

More Information

Corresponding author: E-mial: liuqc@cqu.edu.cn

摘要

摘要: 使用流化床，以95%的甲烷作为还原性气氛，以烧结过程中烧结返矿作为载氧体，研究其在化学链燃烧过程中的反应活性以及烧结返矿在氧化还原循环中的结构特征。对烧结矿原料、还原后以及氧化再生的烧结矿进行形貌结构及物性表征。结果表明，在初始氧化循环过程中，烧结返矿的载氧能力和反应活性有显著的提高；前25个循环过程中，烧结返矿的比表面积显著增大，比表面积的增大是提高烧结返矿反应活性的主要原因之一。随着循环的进行，烧结返矿表面出现裂纹并逐渐加大。Raman检测结果显示，在还原过程中有新的铁晶型，纤铁矿（γ-FeOOH）生成，而纤铁矿（γ-FeOOH）的生成将降低烧结返矿的载氧能力。氧化循环过程中，采用甲烷作为还原性气体，并未发现有碳沉积现象的产生。
- 烧结返矿 /
- 化学链燃烧 /
- 结构特性 /
- 反应活性
Abstract: The reactivity and structural characterizations of the sintered iron ore in redox cycles were investigated. The sintered return fines were selected as oxygen carriers and the chemical looping combustion was tested in a fluidized bed with a reducing atmosphere of 95% methane. The characterizations of structural and physical properties of the sintered raw materials and the reduced and oxidative regenerated samples were conducted. The results reveal that during the initial oxidation cycle, the oxygen carrying capacity and reaction activity of the sinter are improved remarkably. The specific surface area of the sinter increases significantly in the first 25 cycles, which may be one of the main reasons for the reactivity increase of the sinter. During the recycling process, some cracks are formed on the surface of sintered return fines and gradually get development. The Raman results indicate that the new crystalline phase, lepidocrocite (γ-FeOOH), is formed, which will decrease the oxygen carrying capacity of the oxygen carrier. When the methane is used as the reducing gas, there is no carbon deposition on the surface.
- sintered return fines /
- chemical-looping combustion /
- structural characterizations /
- reaction activity

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图 1 化学链燃烧流程示意图

Figure 1 Reaction scheme of CLC process

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图 2 流化床反应器装置示意图

Figure 2 Device diagram of fluidized bed reactor

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图 3 750 ℃下10个循环时各气体组分随时间的变化

Figure 3 Typical product gas distributions in the tenth reduction cycle in the fluidized bed at 750 ℃

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图 4 750 ℃ 时循环次数对气体生成率的影响

Figure 4 Effect of redox cycle numbers on the gas production at 750 ℃

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图 5 750 ℃ 时循环次数对CH₄的转化率的影响

Figure 5 Effect of redox cycle numbers on the conversion of CH₄ at 750 ℃

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图 6 10个循环时温度对CH₄转化率的影响

Figure 6 Effect of temperature on the conversion of CH₄ in the tenth run

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图 7 750 ℃ 时循环次数对载氧体比表面积的影响

Figure 7 Effect of cycle number on the BET surface area of OCs at 750 ℃

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图 8 10个循环时温度对载氧体比表面积的影响

Figure 8 Effect of temperature on the BET surface area of OCs

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图 9 750 ℃时不同循环次数载氧体的表面形貌照片

Figure 9 SEM images of prepared samples

(a): fresh; (b): 20 cycle; (c): 40 cycle

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图 10 烧结返矿的Raman光谱分析

Figure 10 Raman spectra of the oxygen carrier particles

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表 1 原始烧结返矿的主要化学组成

Table 1 Chemical composition of the sintering return fines

Sample Chemical composition w/%

TFe Fe₂O₃ CaO MgO Al₂O₃ SiO₂

Sintering return fines 59.63 85.18 8.40 1.36 1.41 3.41

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