化工学报 ›› 2023, Vol. 74 ›› Issue (6): 2611-2623.DOI: 10.11949/0438-1157.20230254

• 能源和环境工程 • 上一篇    下一篇

基于甲烷脉冲法的Fe2O3-Al2O3载氧体还原特性研究

周小文1,3(), 杜杰2,3, 张战国1,3(), 许光文1,3()   

  1. 1.沈阳化工大学化学工程学院,辽宁 沈阳 110142
    2.沈阳工业大学材料科学与工程学院,辽宁 沈阳 110870
    3.沈阳化工大学资源化工与材料教育部重点实验室,辽宁 沈阳 110142
  • 收稿日期:2023-03-17 修回日期:2023-06-03 出版日期:2023-06-05 发布日期:2023-07-27
  • 通讯作者: 张战国,许光文
  • 作者简介:周小文(1998—),女,硕士研究生,603901789@qq.com
  • 基金资助:
    国家自然科学基金项目(U21A20316)

Study on the methane-pulsing reduction characteristics of Fe2O3-Al2O3 oxygen carrier

Xiaowen ZHOU1,3(), Jie DU2,3, Zhanguo ZHANG1,3(), Guangwen XU1,3()   

  1. 1.Faculty of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
    2.School of Environmental and Chemical Engineering, Shenyang University of Technology, Shenyang 110870, Liaoning, China
    3.Key Laboratory of Resource Chemicals and Materials, Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
  • Received:2023-03-17 Revised:2023-06-03 Online:2023-06-05 Published:2023-07-27
  • Contact: Zhanguo ZHANG, Guangwen XU

摘要:

开发高效廉价铁基载氧体是天然气化学链重整制氢技术走向应用的关键。为探究高效铁基载氧体设计的基本依据,利用自行设计的脉冲反应器和气体产物全量同步在线分析系统,在800℃和无内外扩散影响的条件下研究了不同Fe2O3质量分数的Fe2O3-Al2O3载氧体的甲烷脉冲法还原特性。结果表明:Fe2O3的还原反应依两段机理进行,随载氧体颗粒内Fe2O3含量的多少可停止于Fe3O4,也可完全进行至FeO;气相产物中CO2与CO的摩尔比随CH4脉冲次数的变化规律也与Fe2O3含量密切相关。对用α-Al2O3粉末稀释高Fe2O3质量分数载氧体粉末的方法制备的低Fe2O3质量分数颗粒进行的脉冲还原实验结果,进一步揭示单位时间进入单个载氧体颗粒内的CH4量与其Fe2O3含量的摩尔比决定单个颗粒以及整个床层的Fe2O3还原度。最后对还原度和CH4转化率以及CO2选择性数据进行关联分析,发现只有将载氧体的还原过程止于生成Fe3O4阶段才能得到较高的CO2选择性,从而达到低成本回收高纯CO2的目的。

关键词: 甲烷, 脉冲, 化学链, 制氢, 载氧体, 反应器

Abstract:

Developing a highly efficient and low-priced iron-based oxygen carrier is the key to the application of chemical looping reforming of natural gas for hydrogen production. In order to explore the basic principle of designing such an oxygen carrier, the methane-pulsing reduction characteristics of Fe2O3-Al2O3 oxygen carriers with different Fe2O3 contents were studied at 800℃ and without the influence of external and internal diffusion by using a self-designed reactor system capable of on-line methane pulsing and synchronized analysis of gaseous reaction products. The results show that the reduction reaction of Fe2O3 proceeds according to a two-stage mechanism, which can stop at Fe2O3 or completely proceed to FeO with the content of Fe2O3 in the oxygen carrier particles. The variation pattern of the molar ratio of CO2 to CO in the gas phase product with the number of CH4 pulses is also closely related to the content of Fe2O3. Pulse reduction results of particles prepared from a mixture of α-Al2O3 powder and powdery 80% (mass) Fe2O3-Al2O3 oxygen carrier further reveal that the reduction degree of Fe2O3 in a single particle as well as in the whole bed is determined by the molar ratio of CH4 entering the particle per unit time to the absolute amount of Fe2O3 in the particle. At last analysis on the correlations of the reduction degree of Fe2O3 and CH4 conversion and CO2 selectivity leads to a conclusion that only limiting the reduction process of Fe2O3 oxygen carries to the stage of Fe3O4 formation could yield a reacted stream of a sufficiently high CO2 concentration for low-cost recovery of high purity CO2.

Key words: methane, pulse reaction, chemical looping, hydrogen production, oxygen carrier, reactor

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