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Method for deeply removing impurities of manganese dioxide electrolyte

A manganese dioxide and electrolyte technology, applied in the direction of non-aqueous electrolyte batteries, electrolytic components, electrolytic process, etc., can solve the problems of high cost of impurity removal and poor effect of impurity removal, so as to reduce production cost, reduce burden, realize The effect of economization

Inactive Publication Date: 2014-02-05
GUANGXI GUILIU CHEM CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to overcome the problems of poor impurity removal effect and high cost of impurity removal in the existing electrolytic manganese dioxide electrolyte——the deep removal method of harmful metal ions in manganese sulfate solution. Based on the introduction of Ca (MnO 4 ) 2 , NaMnO 4 MnO in 4 － As an adsorbent, a method for deep removal of impurities in manganese dioxide electrolyte is provided

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) Neutralization and removal of iron: under normal temperature conditions, add calcium carbonate to the crude manganese sulfate slurry to neutralize the residual H in the solution 2 SO 4 , so that the pH of the solution is 5.0, stop adding calcium carbonate, and detect that the concentration of ferrous ions in the solution is ≤10 -5 mol / L is qualified, if the concentration of ferrous ions>10 -5 mol / L, add adsorbent until the content of ferrous ions in the mixed solution is qualified, continue to add calcium carbonate to adjust the pH value to 6.0 after the ferrous ions are qualified, and detect the concentration of ferric ions in the mixed solution ≤ 10 -5 mol / L is qualified, if the concentration of ferric ion>10 -5 mol / L, continue to add calcium carbonate until the ferric ion content in the mixed solution is qualified, filter and remove the filter residue to obtain crude manganese sulfate solution.

[0019] (2) Sulfide precipitation and impurity removal: heat the ...

Embodiment 2

[0024] (1) Neutralization and iron removal: with embodiment 1.

[0025] (2) Sulphide precipitation and impurity removal: heat the crude manganese sulfate solution obtained in step (1) to 85° C., slowly add barium sulfide BaS and sodium sulfide Na 2 Sulfur mixture of S, 30% sodium sulphide Na 2 S solution and 30% barium sulfide BaS solution are mixed according to the volume ratio of 0.1L:0.9L, the speed of adding the vulcanization mixture is 2g / L / min, and the concentration of Cu, Pb, Ni, Co is detected every 30min, when Cu≤ 2ppm, Pb ≤ 3ppm, Ni ≤ 2ppm, Co ≤ 2ppm, stop adding the vulcanization mixture, and filter to obtain the manganese sulfate solution after sulfide precipitation and impurity removal.

[0026] (3) Deep removal of impurities by adsorbent: Add electrolytic waste liquid to the manganese sulfate solution obtained in step (2) to adjust the pH of the reaction solution to 4.5, and add adsorbent to make the concentrations of trace elements As, Sb, and Mo all ≤0.005ppm ...

Embodiment 3

[0030] (1) Neutralization and iron removal: with embodiment 1.

[0031] (2) Sulfide precipitation and impurity removal: heating the crude manganese sulfate solution obtained in step (1) to 88°C, slowly adding barium sulfide BaS and sodium sulfide Na 2 Sulfur mixture of S, 25% sodium sulphide Na 2 S solution and 25% barium sulfide BaS solution are mixed according to the volume ratio of 0.2L:0.8L, the speed of adding the vulcanization mixture is 4g / L / min, and the concentration of Cu, Pb, Ni, Co is detected every 30min, when Cu≤ 2ppm, Pb ≤ 3ppm, Ni ≤ 2ppm, Co ≤ 2ppm, stop adding the vulcanization mixture, and filter to obtain the manganese sulfate solution after sulfide precipitation and impurity removal.

[0032] (3) Deep removal of impurities by adsorbent: Add electrolytic waste liquid to the manganese sulfate solution obtained in step (2) to adjust the pH of the reaction solution to 4.0, and add adsorbent to make the concentrations of trace elements As, Sb, and Mo all ≤0.005p...

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Abstract

The invention belongs to the field of processing of a battery material, and particularly relates to a method for deeply removing impurities of a manganese dioxide electrolyte. The method comprises the following steps: neutralization iron removal, impurity removal by sulfide precipitation, and deep impurity removal of an adsorbent. MnO4<-> in Ca(MnO4)2 and NaMnO4 is led in as an adsorbent on the basis of impurity removal of manganese oxide mineral powder and new manganese dioxide; calcium carbonate CaCO3 is utilized to adjust the pH value of a reaction solution to 4.5 after a manganese sulfate solution is subjected to neutralization iron removal through the calcium carbonate; the adsorbent is added, so that the concentration of trace elements As, Sb and Mo is smaller than or equal to 0.005ppm. By adopting the method, more efficient impurity removal and absorption can be carried out by leading in the MnO4<-> adsorbent; the efficiency of the production technology is improved; an excellent manganese sulfate solution with low impurity content is obtained; a foundation is established for later electrolysis to obtain an excellent manganese dioxide semi-finished product.

Description

technical field [0001] The invention belongs to the field of battery material processing, in particular to a deep impurity removal method for harmful metal ions in electrolytic manganese dioxide electrolyte—manganese sulfate solution. Background technique [0002] The preparation of high-purity manganese sulfate solution is an essential pre-process for the manufacture of electrolytic manganese dioxide (EMD) for alkaline zinc-manganese batteries. The development of alkaline zinc-manganese dry batteries has put forward higher and higher requirements for EMD. Its chemical purity is one aspect of this. According to earlier information, the chemical impurities of EMD that affect battery performance can be divided into active components (Hg); nearly harmless components (Mg, Na, Mn); slightly harmful components (Cd, Fe); quite harmful components ( Ni, Co, Mo, Cu) and the most harmful components (Sb, As). These components not only refer to the quantity, but also are related to...

Claims

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Application Information

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IPC IPC(8): C25B1/21C25B15/08H01M6/14
Inventor 覃胜先吴伟金涂忠益罗冰吴元花张亮乐
Owner GUANGXI GUILIU CHEM CO LTD
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