The Process and Mechanism of Electrolytic Manganese Anode Slime Lead Removal

Abstract:

Production of electrolytic manganese metal inevitably produces a certain amount of solid wasteelectrolytic manganese anode slime, with a high manganese content, but its difficult to recycle due to the presence of other impurities. Firstly, the washing method was used to remove the anode slime soluble salts, then its chemical composition and phase were analyzed. The flame atomic absorption spectrometer and X-ray fluorescence (XRF) analysis showed the anode slime mainly contained Mn, Pb, Ca, Fe, Cr, K, Se and other metal elements, with the average manganese content 45% and the lead 3.5%;X-ray diffraction (XRD) preliminary analysis showed that the anode slime was a colloidal system mainly containing the spinel structure of MnO₂ and complex salts PbMn₈O₁₆xH₂O phase, by high temperature roasting, the anode slime transformed from hexagonal system to cubic system , and the basic structure unit from edges connection to surfaces connection,the change of length,angle and fracture of manganese-oxygen bond provided the channel for the lead leaching;TG-DTA analysis showed that anode slime was dominated by water loss below 400°C,and started to lose oxygen beyond 425°C, and clear endothermic peak was observed at 500°C and 700°C, which showed the anode slime crystal structure changed at 500°C, anode slime weight loss tending to be gentle with some Mn₂O₃ generation at 700°C, and roasted crystal stabilizing to Mn₂O₃. Preliminary roasting and leaching purification technology route was proposed according to the above analysis results, and analysis of the purification process related factors was made. Under the condition of natural ventilation, anode slime was roasted at 700°C, and fully leached in 2mol/L HAc , with liquid-solid ratio 10:1, then leached anode slime was characterized by XRD and flame atomic absorption test, the results showed that anode slime manganese content increased from 45% to 67.5%, the lead content decreased from 3.5% to 0.1%, XRD indicated that the anode slime existing phase was Mn₂O₃. Anode slime after purification treatment can be further used for battery manganese source material, which provides an effective approach for the recovery of manganese anode slime utilization.

• Periodical: Advanced Materials Research (Volume 878)
• Pages: 163-170
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.878.163
• Online since: January 2014
• Authors: Liang Qu Huang, Ya Fan Bi, Lin Lin Mu, Hong Bo Zhang
• Keywords: Anode Slime, Crystal Structure, Electrolytic Manganese, Pb Removal

References

[1] Y.M. Yun, Resources of Mn-ores and development of EMM, China's manganese industry, 22(2004)26-30.

[2] C.Y. Tao, D.H. Li, Z.H. Liu, Activation and purification of electrolytic-manganese anode slime and its application, Battery Bimonthly. 9(2011)121-124.

[3] Y. Qi, J. Luo, W.Z. Tu, Pollution and harness of EMM production, China's manganese industry, 24(2006)42-45.

[4] X.B. Zeng, Electrolysis of manganese abroad, China's manganese industry, 18(2000)7-11.

[5] Y.M. Zhou, G.G. Mei, Study on the anode electrochemical reaction and increase current efficiency from electrolyzing manganese, China's manganese industry. 19(2001)17-19.

[6] Editorial Board of the State Environmental Protection Administration of water and wastewater monitoring and analysis methods. Water and wastewater monitoring and analysis methods, China Environmental Science Press. Bei Jing, 2002, pp.291-298.

[7] G.G. Mei, W.S. Zhang, X.B. Zeng, third ed., Technology of china manganese industry, Central South University Press, Hu Nan, 2011, pp.309-315.

[8] R. Liu, S. Qin, A.H. Lu, third ed., The tunnel structure of manganese oxides and hydroxides and environmental significance, Mineral Petrol, 23(2003)28-33.

[9] Y.Q. Shen, Z.R. Fu, Y.F. Huang, The research on manganese anode slime recycle to produce into chemical manganese dioxide, Journal of Chinese manganese industry. 25(2007)14-16.

[10] Q.M. Huang, C.P. Wang, H. zhou, third ed., The research on manganese anode slime recycled to produce manganese sulfate, Nonferrous Metals (Extractive Metallurgy), (2010)6-8.

[11] S.J. He, T.T. Wei, F.M. Chen, Electrolytic metal manganese anode slime recovery and discharge manganese powder preparation research, Chinese manganese industry. 30(2012)30-32.

[12] J.G. Tang, Z.C. Han, Investigation on process mineralogy of manganese anode slime and impurity removal, Journal of mining and metallurgy. 14(2005)75-78.

[13] P.G. Wang, Y.Q. Shen, Y.Z. Jing, The research status of lithium manganese dioxide batteries-and prospects, Power technology. 4(2012)1058-1061.

[14] X. Xia, Crystal structure, preparation and discharge performance for manganese and related manganese oxides (1), Battery Bimonthly. 34(2004)411-414.

[15] X. Xia, Crystal structure, preparation and discharge performance for manganese and related manganese oxides(2), Battery Bimonthly. 35(2005)27-30.

[16] X. Xia, Crystal structure, preparation and discharge performance for manganese and related manganese oxides(3), Battery Bimonthly. 35(2005)105-108.

[17] L. Huang, Q.X. Zhou, Q.R. Zhang, Removal effects of citric acid, oxalic acid and acetic on Cd, Pb, Cu and Zn in sewage sludge, Chinese Journal of Applied Ecology, 19(2008)641-646.

[18] X.F. Zeng, Z.W. Wang, Heavy metal removal from municipal sludge using acetic acid-ferrite sedimentation method, Environmental Science and Technology, 32 (2009)143-146.

[19] B. Liu,P. S. Thomas, A.S. Ray, R. P. Williams, The effect of sampling conditions on the thermal decompoesition of electrolytic manganese dioxide, Thermal Analysis and Calorimetry. 76(2004)115-122.

DOI: 10.1023/b:jtan.0000027810.56753.0d

[20] Z.R. Fu, Y.Q. Shen, A. H Shi, Manganese anode slime recycled to produce chemical manganese dioxide with calcination-sour soak-oxidation, Jishou University. 28(2007)107-109.