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γ-Fe2O3纳米颗粒尺寸及碳化气氛对碳化过程的影响

樊竞元 吕振刚 张成华 许健 相宏伟

樊竞元, 吕振刚, 张成华, 许健, 相宏伟. γ-Fe2O3纳米颗粒尺寸及碳化气氛对碳化过程的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60157-3
引用本文: 樊竞元, 吕振刚, 张成华, 许健, 相宏伟. γ-Fe2O3纳米颗粒尺寸及碳化气氛对碳化过程的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60157-3
FAN Jing-yuan, LV Zhen-gang, ZHANG Cheng-hua, XU Jian, XIANG Hong-wei. Study on size effect of γ-Fe2O3 nanoparticles and gas atmosphere on carburization process[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60157-3
Citation: FAN Jing-yuan, LV Zhen-gang, ZHANG Cheng-hua, XU Jian, XIANG Hong-wei. Study on size effect of γ-Fe2O3 nanoparticles and gas atmosphere on carburization process[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60157-3

γ-Fe2O3纳米颗粒尺寸及碳化气氛对碳化过程的影响

doi: 10.1016/S1872-5813(21)60157-3
基金项目: 国家自然科学基金(91545109)资助
详细信息
    作者简介:

    樊竞元:fanjingyuan18@mails.ucas.ac.cn

    通讯作者:

    Tel:+86-6977-3996,E-mail:xujian@synfuelschina.com.cn

  • 中图分类号: O643

Study on size effect of γ-Fe2O3 nanoparticles and gas atmosphere on carburization process

Funds: The project was supported by National Natural Science Foundation of China (91545109)
  • 摘要: 采用油酸铁热分解法制备出不同尺寸(4−19 nm)的γ-Fe2O3纳米颗粒,在350 ℃下,于5%CO/He、5%CO/10%H2/He和5%CO/20%H2/He的三种气氛中,使用原位XRD反应装置研究了γ-Fe2O3纳米颗粒的碳化过程与物相变化规律,同时结合Raman、CO-TPR和TEM等手段对样品进行了表征。结果表明,γ-Fe2O3纳米颗粒完全碳化后会形成稳定比例的χ-Fe5C2和θ-Fe3C的混合相;在相同碳化气氛下,随γ-Fe2O3颗粒尺寸增大完全碳化所需时间缩短,尺寸较小的γ-Fe2O3颗粒表面残留碳较多,会抑制碳化反应进程,碳化相中θ-Fe3C相对含量随γ-Fe2O3纳米颗粒尺寸增大而增高;相同尺寸的γ-Fe2O3颗粒在不同气氛下碳化,完全碳化所需时间随H2分压增大先缩短后略有延长,碳化相中θ-Fe3C相对含量随H2分压增大而增高。通过调节γ-Fe2O3颗粒尺寸和碳化气氛可定向制得合适比例的χ-Fe5C2和θ-Fe3C混合相,这一结果有益于费托合成铁基催化剂中的铁碳化物活性相结构的优化。
  • 图  1  不同尺寸γ-Fe2O3纳米颗粒XRD谱图

    Figure  1  XRD patterns of γ-Fe2O3 nanoparticles of different sizes

    图  2  不同尺寸γ-Fe2O3纳米颗粒Raman谱图

    Figure  2  Raman spectrum of γ-Fe2O3 nanoparticles of different sizes

    图  3  γ-Fe2O3纳米颗粒TEM图及其颗粒尺寸分布

    Figure  3  Distribution graph and TEM images of γ-Fe2O3 nanoparticles of different sizes

    图  4  350 ℃下不同尺寸γ-Fe2O3纳米颗粒Raman谱图

    Figure  4  Raman spectrum of γ-Fe2O3 nanoparticles of different sizes at 350 ℃

    图  5  不同尺寸γ-Fe2O3纳米颗粒的CO-TPR谱图

    Figure  5  CO-TPR profiles of γ-Fe2O3 nanoparticles of different sizes

    图  6  350 ℃下,10 nm的γ-Fe2O3颗粒在5%CO/20%H2/He碳化后χ-Fe5C2与θ-Fe3C混合相XRD谱图

    Figure  6  XRD patterns of mixed phase of χ-Fe5C2 and θ-Fe3C after carburization of γ-Fe2O3 particles with 10 nm at 350 ℃ in 5%CO /20%H2/He

    图  7  270 ℃下10 nm的γ-Fe2O3在5%CO/He中碳化产物相对含量图

    Figure  7  Relative abundance of carburization products of γ-Fe2O3 with 10 nm at 270 ℃ in 5%CO/He

    图  8  300 ℃下10 nm的γ-Fe2O3在5%CO/He中碳化产物相对含量图

    Figure  8  Relative abundance of carburization products of γ-Fe2O3 with 10 nm at 300 ℃ in 5%CO/He

    图  9  350 ℃下10 nm的γ-Fe2O3在5%CO/He中碳化产物相对含量图

    Figure  9  Relative abundance of carburization products of γ-Fe2O3 with 10 nm at 350 ℃ in 5%CO/He

    图  10  350 ℃下4 nm的γ-Fe2O3在5%CO/10%H2/He中碳化产物相对含量图

    Figure  10  Relative abundance of carburization products of γ-Fe2O3 with 4 nm at 350 ℃ in 5%CO/10%H2/He

    图  11  350 ℃下10 nm的γ-Fe2O3在5%CO/10%H2/He中碳化产物相对含量图

    Figure  11  Relative abundance of carburization products of γ-Fe2O3 with 10 nm at 350 ℃ in 5%CO/10%H2/He

    图  12  350 ℃下19 nm的γ-Fe2O3在5%CO/10%H2/He中碳化产物相对含量图

    Figure  12  Relative abundance of carburization products of γ-Fe2O3 with 19 nm at 350 ℃ in 5%CO/10%H2/He

    图  13  350 ℃下4 nm的γ-Fe2O3在5%CO/20%H2/He中碳化产物相对含量图

    Figure  13  Relative abundance of carburization products of γ-Fe2O3 with 4 nm at 350 ℃ in 5%CO/20%H2/He

    图  14  350 ℃下10 nm的γ-Fe2O3在5%CO/20%H2/He中碳化产物相对含量图

    Figure  14  Relative abundance of carburization products of γ-Fe2O3 with 10 nm at 350 ℃ in 5%CO/20%H2/He

    图  15  350 ℃下19 nm的γ-Fe2O3在5%CO/20%H2/He中碳化产物相对含量图

    Figure  15  Relative abundance of carburization products of γ-Fe2O3 with 19 nm at 350 ℃ in 5%CO/20%H2/He

    表  1  350 ℃下不同尺寸γ-Fe2O3在不同气氛下完全碳化所需时间及碳化产物分布表

    Table  1  The time required for complete carburization of different sizes of γ-Fe2O3 in different atmospheres and the distribution of carburization products at 350 ℃

    Samples5%CO/He w/%5%CO/10%H2/He w/%5%CO/20%H2/He w/%
    4 nm15 h4 h3.5 h
    Fe5C2(0%)Fe5C2(85%)Fe5C2(65%)
    Fe3C (0%)Fe3C (15%)Fe3C (35%)
    10 nm5 h1 h0.5 h
    Fe5C2(80%)Fe5C2(60%)Fe5C2(50%)
    Fe3C (20%)Fe3C (40%)Fe3C (50%)
    19 nm3 h1.3 h1.3 h
    Fe5C2(20%)Fe5C2(60%)Fe5C2(55%)
    Fe3C (80%)Fe3C (40%)Fe3C (45%)
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  • 收稿日期:  2021-07-08
  • 修回日期:  2021-08-21
  • 网络出版日期:  2021-09-19

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