Review on research progress of high purity vanadium pentoxide preparation by chlorination process
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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。Abstract: As a crucial raw material for all-vanadium redox flow battery(VRFB), the high purity vanadium pentoxide (V2O5) is under an increasingly urgent demand with the rapid development of VRFB in recent years. Based on this background, a plenty of processes have been proposed for high purity V2O5 preparation, among which the chlorination process is paid more and more attentions due to the remarkable advantages of high efficiency, favorable selectivity, high purity of products and eco-friendly feature. In this paper, we reviewed the research progress with relevant literatures concentrated on the three key procedures of high purity V2O5 preparation via chlorination process, including thermodynamics, kinetics and processes of chlorination of raw materials, purification of crude vanadium oxytrichloride (VOCl3) and conversion of VOCl3 into V2O5. The high-efficient utilization of secondary vanadium resources, the selective hydrolysis of crude vanadium oxychloride to remove TiCl4 and conversion of VOCl3 into V2O5 by catalytic oxidation are proposed as the development trends of the corresponding key procedures. Finally, carrying out the pilot test and developing the key equipment for preparing high-purity vanadium pentoxide by chlorination process are the key and difficult points for realizing the industrial production in the future.
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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 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
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 
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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。
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