Study on leaching behavior of vanadium in acid leaching process of calcium and manganese vanadate system
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摘要: 钒酸钙和钒酸锰是钒渣钙化焙烧过程中重要的焙烧产物，其在硫酸中的溶解浸出行为对提钒过程钒收率有重要影响。采用单因素试验递进式研究了浸出pH值、时间及温度对合成钒酸钙（锰）以及钒渣钙化（锰化）、钙锰复合焙烧熟料中钒组元浸出行为的影响。结果表明，合成CaV2O6、Ca2V2O7、Ca3V2O8及Mn2V2O7在pH值分别为3.0、3.0、5.0、2.2的硫酸溶液中于60 ℃下浸出60 min时，钒的浸出率达到最大值，分别为43.62%、98.79%、97.98%、98.06%。pH值为1.0～2.0时，四种钒酸盐钒的浸出率均出现一个低谷，这是由钒的水解引起的。钒渣常规钙化和锰化焙烧过程中主要生成Ca2V2O7和Mn2V2O7两种钒酸盐，浸出pH值为2.5时，钒的浸出率分别为85.24%、87.07%；钒渣钙锰复合焙烧过程中生成的焦钒酸钙、焦钒酸锰共生复盐，熟料于pH值为2.5的硫酸溶液中浸出后钒的浸出率最大为90.09%，较常规钙化、锰化体系钒的浸出率高约四个百分点，表明钙、锰协同提钒与单一添加剂提钒相比有一定的强化作用。Abstract: Calcium vanadate and manganese vanadate are important roasting products in the calcification roasting process of vanadium slag, and their dissolution and leaching behavior in sulfuric acid has an important effect on the vanadium yield in the vanadium extraction process. In this paper, the effects of leaching pH, time and temperature on the leaching behavior of vanadium components in the synthesis of calcium vanadate (or manganese vanadate), vanadium slag calcification (or reaction with manganese) and calcium-manganese composite roasting clinker were studied by single factor test step-by-step method. The results showed that the maximum leaching rate of vanadium was 43.62%, 98.79%, 97.98% and 98.06% when the synthetic CaV2O6, Ca2V2O7, Ca3V2O8 and Mn2V2O7 were leached at 60℃ for 60 min at pH 3.0, 3.0, 5.0 and 2.2, respectively. When the pH value is 1.0～2.0, the leaching rate of the four vanadates shows a low peak, which is caused by the hydrolysis of vanadium. Ca2V2O7 and Mn2V2O7 vanadate were mainly formed during the conventional calcification and manganese roasting of vanadium slag, and the leaching rates of vanadium were 85.24% and 87.07%, respectively, when the leaching pH value was 2.5. The leaching rate of vanadium after clinker leaching in sulfuric acid solution with pH value of 2.5 was 90.09%, which was about four percentage points higher than that of vanadium in conventional calcification and manganese systems, indicating that the synergistic extraction of vanadium from calcium and manganese had a certain strengthening effect on vanadium extraction with a single additive.
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Key words:
- vanadium slag /
- calcification roasting /
- calcium vanadate /
- manganese vanadate /
- leaching behavior
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图 2 合成钒酸盐CaV2O6、Ca2V2O7、Ca3V2O8和Mn2V2O7的X射线衍射谱
Figure 2. XRD patterns of as-syntheszed CaV2O6、Ca2V2O7、Ca3V2O8 and Mn2V2O7
图 3 钒渣钙化、锰化及钙锰复合焙烧熟料的X射线衍射谱
Figure 3. XRD patterns of roasted samples of vanadium slag with calcification， manganese，calcium-manganese
图 4 pH值对三种钒酸钙在硫酸溶液中钒浸出率的影响
Figure 4. Effect of pH value on the leaching rate of vanadium of CaV2O6、Ca2V2O7、Ca3V2O8 in sulfuric acid
图 5 硫酸溶液的pH值对钒的存在形式及浓度的影响
Figure 5. Effect of pH value of sulfuric acid solution on the form and concentration of vanadium
图 6 硫酸溶液pH值对Ca2V2O7和Mn2V2O7钒浸出率的影响
Figure 6. Effect of pH value on the leaching rate of vanadium of Ca2V2O7 and Mn2V2O7 in sulfuric acid
图 7 浸出时间对三种钒酸钙在硫酸中钒浸出率的影响
Figure 7. Effect of leaching time on the vanadium leaching rate of CaV2O6、Ca2V2O7、Ca3V2O8 in sulfuric acid
图 8 浸出时间对焦钒酸锰在硫酸中钒浸出率的影响
Figure 8. Effect of leaching time on the leaching rate of vanadium of Mn2V2O7 in sulfuric acid
图 9 pH值为1.5时三种钒酸钙及焦钒酸锰硫酸浸出尾渣的X射线衍射谱
Figure 9. XRD patterns of sulfuric acid leaching tailings of calcium vanadate and Mn2V2O7 at pH=1.5
图 10 浸出时间对Ca2V2O7和Mn2V2O7硫酸中钒浸出率的影响
Figure 10. Effect of leaching time on the vanadium leaching rate of Ca2V2O7 and Mn2V2O7 in sulfuric acid
图 11 浸出温度对Ca2V2O7和Mn2V2O7硫酸中钒浸出率的影响
Figure 11. Effect of leaching temperature on the vanadium leaching rate of Ca2V2O7 and Mn2V2O7 in sulfuric acid
图 12 pH值对钒渣体系硫酸浸出过程钒浸出率的影响
Figure 12. Effect of pH value on the vanadium leaching rate of vanadium slag system in sulfuric acid
图 13 pH为2.5时钒渣钙化、锰化体系浸出尾渣的XRD分析
Figure 13. XRD patterns of calcification roasting-acid leaching residue and manganese roasting-acid leaching residue at pH=2.5
图 14 pH值对钒渣钙锰复合体系钒浸出率的影响
Figure 14. Effect of pH value on the vanadium leaching rate of vanadium slag calcium-manganese system
图 15 pH=2.5时钒渣钙锰复合体系浸出尾渣的XRD分析
Figure 15. XRD pattern of calcium-manganese system leaching tailings of vanadium slag at pH = 2.5
图 16 pH=2.5时钒渣钙锰复合体系浸出尾渣的微观形貌及元素分布
Figure 16. (a)～(b) Micromorphology of leaching tailings; (c)～(d) Elemental distribution of leaching tailings from vanadium slag in calcium-manganese system at pH = 2.5
表 1 钒渣主要化学成分
Table 1. Main chemical constituents of vanadium slag
% FeO V2O3 MnO TiO2 CaO Cr2O3 SiO2 Total 38.78 14.81 8.75 11.44 2.47 2.19 14.30 92.74 
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