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氯化法制备高纯五氧化二钒技术研究进展

李卓臣 杜光超 范川林 朱庆山

李卓臣, 杜光超, 范川林, 朱庆山. 氯化法制备高纯五氧化二钒技术研究进展[J]. 钢铁钒钛, 2021, 42(1): 8-15, 92. doi: 10.7513/j.issn.1004-7638.2021.01.002
引用本文: 李卓臣, 杜光超, 范川林, 朱庆山. 氯化法制备高纯五氧化二钒技术研究进展[J]. 钢铁钒钛, 2021, 42(1): 8-15, 92. doi: 10.7513/j.issn.1004-7638.2021.01.002
Li Zhuochen, Du Guangchao, Fan Chuanlin, Zhu Qingshan. Review on research progress of high purity vanadium pentoxide preparation by chlorination process[J]. IRON STEEL VANADIUM TITANIUM, 2021, 42(1): 8-15, 92. doi: 10.7513/j.issn.1004-7638.2021.01.002
Citation: Li Zhuochen, Du Guangchao, Fan Chuanlin, Zhu Qingshan. Review on research progress of high purity vanadium pentoxide preparation by chlorination process[J]. IRON STEEL VANADIUM TITANIUM, 2021, 42(1): 8-15, 92. doi: 10.7513/j.issn.1004-7638.2021.01.002

氯化法制备高纯五氧化二钒技术研究进展

doi: 10.7513/j.issn.1004-7638.2021.01.002
基金项目: 国家自然科学基金项目(51774262, 22078342, 21736010)。
详细信息
    作者简介:

    李卓臣(1996—),男,四川绵阳人,在读硕士,主要从事高钙钒渣提钒研究,E-mail:zcli19@ipe.ac.cn

    通讯作者:

    范川林(1983—),男,广西玉林人,副研究员,主要从事高纯氧化物粉体及其产品工程的应用基础研究和技术开发,E-mail:chlfan@ipe.ac.cn

  • 中图分类号: TF841.3

Review on research progress of high purity vanadium pentoxide preparation by chlorination process

  • 摘要: 随着全钒液流电池等产业的快速发展,作为关键原料的高纯五氧化二钒,其需求日益增加。在高纯五氧化二钒的众多制备工艺中,氯化法因具有高效清洁、选择性高、产品纯度高等显著优势受到越来越多的关注。针对氯化法制备高纯五氧化二钒的三个关键技术环节:钒原料氯化过程的热力学、动力学和氯化工艺、粗三氯氧钒精制以及三氯氧钒转化制备五氧化二钒的研究进展结合相关文献进行系统评述,其中二次钒资源的高效利用,粗三氯氧钒选择性水解四氯化钛以及三氯氧钒催化氧化制备高纯五氧化二钒是各环节未来的发展方向,此外,开展氯化法制备高纯五氧化二钒的中间试验及关键装备技术的开发是未来实现产业化生产的重点及难点。
  • 图  1  V2O5氯化反应标准吉布斯自由能变化

    Figure  1.  Standard Gibbs free energy change for chlorination reactions of V2O5

    图  2  V-O-Cl不同温度下区域优势图

    (a) 900 K; (b) 1 073 K; (c) 1 273 K; (d) 1 673 K

    Figure  2.  Predominance diagram for the system V-O-Cl at different temperatures

    图  3  VOCl3与主要杂质氯化物的饱和蒸气压曲线

    Figure  3.  Saturated vapor pressure diagram of VOCl3 and the main impurity chlorides

    图  4  (a)不同温度下热力学平衡组成 (b)不同用水量下TiCl4热力学平衡组成[26]

    Figure  4.  Thermodynamic equilibrium compositions of the hydrolysis system of VOCl3 and TiCl4 at (a) various temperatures with fixed water dosage and (b) 80 ℃ with various water dosages[26]

    图  5  部分氯化物水解反应吉布斯自由能

    Figure  5.  Gibbs free energy changes for hydrolysis reaction of chlorides

    图  6  (a)不同用水量下热力学平衡组成;(b)200 ℃和500 ℃下不同H2O/VOCl3下产物氯含量及产率[32]

    Figure  6.  (a) Thermodynamic equilibrium compositions for gaseous hydrolysis of VOCl3 at different water dosages; (b) The Cl content of the product and the yield rate as functions of the H2O/VOCl3 molar ratio at 200 and 500 ℃[32]

    图  7  三氯氧钒催化氧化反应机理

    Figure  7.  Schematic diagram for catalytic oxidation of VOCl3

    表  1  不同氯化体系动力学参数

    Table  1.   Kinetics parameters of different chlorination systems

    氯化体系反应级数温度/℃活化能/(kJ·mol−1)控制步骤
    Cl2+N2 0.78 <570 235 化学反应
    570<T<650 77 化学反应,内扩散
    Cl2+CO+N2 <650 100 化学反应
    >680 105 化学反应
    CCl4 0.5 77±5 化学反应
    下载: 导出CSV

    表  2  不同钒原料氯化反应条件及钒的氯化率

    Table  2.   Parameters and vanadium extraction ratio for chlorination of different vanadium raw materials

    含钒原料氯化剂反应器类型氯化温度/℃时间/h钒氯化率/%反应方程
    工业级五氧化二钒 AlCl3 固定床 170 2 83 1/2V2O5+AlCl3→VOCl3+1/2Al2O3
    钒渣 Cl2 流化床 650 2 87 1/5Mn2V2O7+Cl2+1/2C→2/5MnCl2+2/5VOCl3+1/2CO2
    含钒废催化剂 Cl2 固定床 400~550 0.5 73 1/3V2O5+Cl2→2/3VOCl3+1/2O2
    钒钛磁铁矿 FeCl2 固定床 827 2 22 1/2V2O5+FeCl3→ VOCl3+1/2Fe2O3
    FeCl3 827 2 32 1/3V2O5+FeCl2+1/4O2→ 2/3VOCl3+1/2Fe2O3
    石煤 Cl2 固定床 1000 1 90 1/3V2O3+Cl2→2/3VOCl3+1/6O2
    注:钒渣预处理工艺为900 ℃预氧化2 h;钒钛磁铁矿预处理工艺为900 ℃预氧化2 h;石煤预处理工艺为600 ℃预脱碳2 h。
    下载: 导出CSV
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  • 收稿日期:  2020-12-18
  • 刊出日期:  2021-02-10

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