Hydrometallurgy leaching of manganese from electrolytic manganese anode slime using hydrogen peroxide as reducing agent
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摘要: 電解錳陽極泥是生產電解金屬錳時陽極產生的副產物，其中含有大量錳、鉛等資源。如何高效浸出電解錳陽極泥中的錳是實現其資源化利用的關鍵，本研究提出了一種H2SO4?H2O2浸出體系強化電解錳陽極泥中錳浸出的新方法，研究了H2O2和H2SO4用量、反應溫度、反應時間以及固液比對電解錳陽極泥中錳浸出率的影響。研究結果表明，在陽極泥與H2O2質量比1∶0.8、陽極泥與H2SO4質量比1∶0.9、反應溫度45 ℃、固液質量比1∶10條件下浸出反應15 min，錳的浸出率可達97.23%，浸出渣中Pb的質量分數高達53.71%。浸出機理分析表明，酸性條件下電解錳陽極泥中錳氧化物被H2O2還原浸出，浸出液中Mn主要以MnSO4存在，浸出渣中Pb主要以PbSO4富集。本研究結果為電解錳陽極泥的資源化利用提供了一種新思路。Abstract: Manganese is one of the important strategic resources in China, and there is a saying that “no manganese, no steel”. In 2020, China’s output of electrolytic metal manganese was 1501300 tons, accounting for 96.5% of the global output. At present, manganese metal is mainly obtained using the electrodeposition process. Electrolytic manganese anode slime (EMAS) is a kind of solid waste generated during the production of electrolytic metal manganese, which contains a significant amount of manganese, lead, and other resources. Every year, 60000?180000 tons of EMAS will be discharged in China, and direct discharge will cause severe environmental pollution. Cleaning and efficiently leaching Mn from EMAS is the key to realizing its resource utilization. A large number of studies have achieved efficient leaching of manganese from EMAS. Still, there are a number of issues, such as complicated processes, high leaching cost, a large amount of reducing agent, and residual organic matter in the leaching solution. Therefore, it is urgent to find a new method for efficient clean leaching of manganese from EMAS. This study proposed a new method of enhancing manganese leaching from EMAS with an H2SO4–H2O2 leaching system. The effects of the dosage of H2SO4 and H2O2, reaction temperature, reaction time, and solid–liquid ratio on the leaching efficiency of manganese from EMAS were studied. The results show that the leaching efficiency of manganese was 97.23%, and the content of Pb in the leaching residue was 53.71%, when the mass ratio of EMAS to H2O2 was 1∶0.8, the mass ratio of EMAS to H2SO4 was 1∶0.9, the leaching temperature was 45 ℃, the solid–liquid mass ratio was 1∶10 and the leaching time was 15 min. Leaching mechanism analysis showed that manganese oxide leaching in EMAS was reduced by H2O2 under acidic conditions, and Mn mainly exists in the leaching solution as MnSO4, as well as Pb in leaching residue is mainly enriched with PbSO4. This study offers a new idea for resource utilization of EMAS.
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Key words:
- electrolytic manganese anode slime /
- leaching efficiency /
- H2O2 /
- Pb /
- leaching mechanism
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圖 1 電解錳陽極泥與H2O2質量比對錳浸出率的影響
（固液比1∶10，電解錳陽極泥與H2SO4質量比1∶0.9，浸出溫度45 ℃，浸出時間60 min）
Figure 1. Effect of the mass ratio of electrolytic manganese anode slime (EMAS) to H2O2 on the manganese leaching efficiency in EMAS
(The solid–liquid mass ratio was 1∶10, the mass ratio of EMAS and H2SO4 was 1∶0.9, the leaching temperature was 45 ℃, and the leaching time was 60 min)
圖 2 電解錳陽極泥與H2SO4質量比對陽極泥中錳浸出率的影響
（固液比1∶10，電解錳陽極泥與H2O2質量為1∶0.8，浸出溫度45 ℃，浸出時間60 min）
Figure 2. Effect of the mass ratio of electrolytic manganese anode slime (EMAS) to H2SO4 on the manganese leaching efficiency in EMAS
(The solid–liquid mass ratio was 1∶10, the mass ratio of EMAS to H2O2 was 1∶0.8, the leaching temperature was 45 ℃, and the leaching time was 60 min)
圖 3 反應溫度對陽極泥中錳浸出率的影響
（固液比1∶10，電解錳陽極泥與H2SO4質量比1∶0.9，電解錳陽極泥與H2O2質量比1∶0.8，浸出時間60 min）
Figure 3. Effect of reaction temperature on the manganese leaching efficiency in electrolytic manganese anode slime (EMAS)
(The solid–liquid mass ratio was 1∶10, the mass ratio of EMAS to H2SO4 was 1∶0.9, the mass ratio of EMAS to H2O2 was 1∶0.8, and the leaching time was 60 min)
圖 4 固液比對陽極泥中錳浸出率的影響
（電解錳陽極泥與H2SO4質量1∶0.9，電解錳陽極泥與H2O2質量比1∶0.8，浸出溫度45 ℃，浸出時間60 min）
Figure 4. Effect of solid–liquid mass ratio on the manganese leaching efficiency in electrolytic manganese anode slime (EMAS)
(The mass ratio of EMAS to H2SO4 was 1∶0.9, the mass ratio of EMAS to H2O2 was 1∶0.8, the leaching temperature was 45 ℃, and the leaching time was 60 min)
圖 5 反應時間對陽極泥中錳浸出率的影響
（固液比1∶10，電解錳陽極泥與H2SO4質量比1∶0.9，電解錳陽極泥與H2O2質量比1∶0.8，浸出溫度45 ℃）
Figure 5. Effect of reaction time on manganese leaching efficiency in electrolytic manganese anode slime (EMAS)
(The solid–liquid mass ratio was 1∶10, the mass ratio of EMAS to H2SO4 was 1∶0.9, the mass ratio of EMAS to H2O2 was 1∶0.8, and the leaching temperature was 45 ℃)
圖 6 原電解錳陽極泥（a）和最優條件浸出渣（b）XRD物相分析
Figure 6. X-ray diffraction phase analysis of raw electrolytic manganese anode slime (EMAS) (a) and leaching residue under optimal conditions (b)
圖 7 原電解錳陽極泥(a)和最優條件下浸出渣(b) SEM-EDS分析
Figure 7. Scanning electron microscopy–energy-dispersive X-ray spectrometry analysis of the raw electrolytic manganese anode slime (EMAS) (a) and leaching residue under optimal conditions (b)
圖 8 原電解錳陽極泥(a)和最優條件浸出渣(b)紅外吸收光譜圖
Figure 8. Infrared absorption spectra of raw electrolytic manganese anode slime (EMAS) (a) and leaching residue under optimal conditions (b)
表 1 電解錳陽極泥化學成分分析（質量分數）
Table 1. Chemical composition analysis of electrolytic manganese anode slime
% Category of EMAS MnO PbO Fe2O3 SnO2 CaO SeO2 Other Raw EMAS 76.54 5.71 0.07 0.06 2.01 0.27 15.34 Leaching EMAS# 1.90 57.85 6.14 1.48 0.43 0.53 31.67 Note: # When the mass ratio of electrolytic manganese anode slime (EMAS) to H2O2 was 1∶0.8, the mass ratio of EMAS to H2SO4 was 1∶0.9, the leaching temperature was 45 ℃, the solid–liquid mass ratio was 1∶10, and the leaching time was 15 min. 
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