Study on preparation of VOSO4 by chemical synthesis of sodium metavanadate
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摘要: 硫酸氧钒（VOSO4）电解液是钒电池中电化学反应的活性物质和能量载体，其品质直接影响钒电池的能量效率、能量密度和使用寿命等性能。以偏钒酸钠（NaVO3）为原料，亚硫酸钠（Na2SO3）为还原剂，通过还原、沉淀、酸溶、结晶工艺制得了VOSO4产物，探索了各因素对钒回收率的影响，并对中间产物VO(OH)2和VOSO4产物进行表征。结果表明：偏钒酸钠浸出液以m(V):m(S)为1:0.5加入亚硫酸钠，在pH为2.5的溶液中于70 ℃恒温下还原60 min后，实现了钒（V）还原为钒（IV）。将pH调至7.0，并在20 ℃下反应10 min，蓝色溶液可转化成VO(OH)2中间产物，此时钒回收率最高，为98.51%。VO(OH)2由直径为50～200 nm球状结构组成，将其用硫酸溶解可得蓝色VOSO4溶液，烘干结晶后得到平均直径为5 μm的固体VOSO4晶体，产物品质符合国标二级标准。该研究为利用钒渣钠化焙烧浸出液原位制备VOSO4提供了前期试验基础。Abstract: Vanadium sulfate (VOSO4) electrolyte is the active material and energy carrier of electrochemical reaction in vanadium battery, and its quality directly affects the performance of vanadium battery such as energy efficiency, energy density and service life. In this paper, VOSO4 was synthesized from sodium metavanadate (NaVO3) and sodium sulfite (Na2SO3) by reduction, precipitation, acid dissolution and crystallization. The effects of various factors on vanadium recovery were investigated, and the intermediate products VO(OH)2 and VOSO4 were characterized. The results show that vanadium (V) can be reduced to vanadium (IV) by adding sodium sulfite into the leaching solution of sodium metavanadate with a mass ratio of m(V):m(S) of 1:0.5 and keeping it at 70 ℃ for 60 min in a solution with pH 2.5. When pH value was adjusted to 7.0 and the reaction temperature was 20 ℃ for 10 min, the blue solution could be converted into VO(OH)2 intermediate product, achieving a highest vanadium recovery of 98.51%. The diameter of VO(OH)2 spherical structure was 50~200 nm. Blue VOSO4 solution can be obtained by dissolving VO(OH)2 with sulfuric acid. After drying and crystallizing, VOSO4 crystal with an average diameter of 5 μm was obtained, and the quality of the product met the second grade standard of national standard. This study provides a preliminary experimental basis for in-situ preparation of VOSO4 from sodium leaching solution of vanadium slag.
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Key words:
- VOSO4 /
- sodium metavanadate /
- vanadium battery electrolyte /
- VO(OH)2 /
- vanadium recovery rate
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图 1 偏钒酸钠制备VOSO4工艺流程
Figure 1. Process flow chart of preparing VOSO4 with sodium metavanadate
图 2 不同还原条件对钒回收率的影响
Figure 2. Effects of different reduction conditions on vanadium recovery
图 3 不同亚硫酸钠用量对钒回收率的影响
Figure 3. Effect of different sodium sulfite dosage on vanadium recovery rate
图 4 不同沉淀条件对钒回收率的影响
Figure 4. Effects of different precipitation conditions on vanadium recovery rate
图 5 偏钒酸钠为钒源所得VO(OH)2的FTIR表征
Figure 5. FTIR diagram of VO(OH)2 obtained from sodium metavanadate as vanadium source
图 6 偏钒酸钠为钒源所得VO(OH)2的SEM-EDS表征
(a)10 000倍；(b)30 000倍；(c) EDS； (d) EDS结果分析
Figure 6. SEM-EDS diagram of VO(OH)2 obtained from sodium metavanadate as vanadium source
图 8 不同沉淀条件下VOSO4的XRD结果
Figure 8. XRD spectra of VOSO4 under different precipitation conditions
图 9 偏钒酸钠为钒源所得VOSO4的SEM-EDS表征
(a)2 000倍；(b)5 000倍；(c) EDS；(d) EDS结果分析
Figure 9. SEM-EDS diagrams of VOSO4 obtained from sodium metavanadate as vanadium source
表 1 中间产物V离子和Na离子含量
Table 1. Content of V4+ and Na+ in intermediate products
g/L V4+ Na+ 洗涤前 30.6 0.69 洗涤后 30.2 0.02 
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表 2 VOSO4产物主要离子含量
Table 2. Main ions content in VOSO4 product
mg/L 成分 V2O5 SO42− Na+ 国标二级 ≥ 136500 ≥ 220800 ≤200 产物 136500 343400 166
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