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Method for preparing battery-grade manganese sulfate from manganese oxide ore

A manganese oxide ore, battery-level technology, applied in the field of hydrometallurgy, can solve the problems affecting the recovery efficiency of manganese sulfate, complex process, high difficulty, etc., and achieve the effects of improving impurity removal effect, improving recovery rate and low cost

Active Publication Date: 2022-03-11
湖南烯富环保科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Paper "He Yinhui, Zhang Haijing, Xiong Shan.MnSO 4 Solution purification and preparation of battery-grade high-purity manganese sulfate [J]. Hydrometallurgy, 2019, 38(5): 380-384)" provides a purification process for manganese sulfate solution, mainly including jarosite removal K and Na, oxidation method to remove iron, manganese fluoride to remove Ca and Mg, sulfide to remove heavy metals and other processes, although K, Na, Ca, Mg, Fe, Cu, Zn, Pb and other impurities have reached very low, but the solution Fluoride ions are not removed, in addition, the process is long and complicated
Patent 201810016993.X provides a recrystallization method to remove calcium from manganese sulfate, but it is difficult to make the calcium and magnesium in the product meet the high-end battery material standards by recrystallization; He Yulin et al. (He Yulin, Li Fujie, Luo Zhihong, Luo Kun .Research on the preparation of battery-grade manganese sulfate by high-temperature crystallization and purification of industrial manganese sulfate[J].Mining and Metallurgy Engineering, 2019,39(3):85-88) Through three times of crystallization and purification, the impurity content in manganese sulfate reached the battery-grade standard. However, multiple crystallization not only consumes a lot of energy, but also seriously affects the recovery efficiency of manganese sulfate

Method used

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  • Method for preparing battery-grade manganese sulfate from manganese oxide ore
  • Method for preparing battery-grade manganese sulfate from manganese oxide ore
  • Method for preparing battery-grade manganese sulfate from manganese oxide ore

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0141] Example 1, Preparation of Battery Grade Manganese Sulfate Using Corn Cob as Biomass Reductant Pyrolulurite Leaching Solution

[0142] The pyrolusite treated in this embodiment has the characteristics of high Ca and Mg contents, the Ca content is 8.51%, and the Mg content is 6.77%.

[0143] Step 1: Reductive acid leaching in a sulfuric acid solution with corncobs as a reducing agent, and obtaining the reduced leaching residue and acid leaching solution after filtration.

[0144] ① Add 400 mesh (about 38um) corncobs and pyrolusite with a particle size of less than 150um and 22% Mn grade into a 3mol / L sulfuric acid solution. The mass ratio of pyrolusite to corncobs is 1:1, and the liquid-solid ratio of the solution is Immediately, the solution was heated to 90°C and reacted for 4 hours. In order to maintain the volume of the solution, water was replenished once after 1 hour of reaction;

[0145] ②Place the heat treatment of the leaching slag in a high-temperature furnace ...

Embodiment 2

[0159] Compared with embodiment 1, the processing technology of step one is adjusted, and the step one of difference is:

[0160] Reductive acid leaching in sulfuric acid solution with rice straw as a reducing agent, and after filtration, the reduction leaching residue and acid leaching solution are obtained.

[0161] ① Add 400 mesh (about 38um) straw and pyrolusite with a particle size of less than 150um and a Mn grade of 22% into a 3mol / L sulfuric acid solution. The mass ratio of pyrolusite to corn cob is 1:1, and the liquid-solid ratio of the solution is 5:1; Immediately, heat the solution to 90°C and react for 4 hours. In order to maintain the volume of the solution, add water once after 1 hour of reaction; after the reaction, filter to obtain the acid leaching solution and leaching residue;

[0162]② Place the heat treatment of the leaching slag in a high-temperature furnace isolated from air, raise the temperature to 1000°C at a heating rate of 15°C / min, and then keep it...

Embodiment 3

[0168] Compared with Example 1, the only difference is that the compound of formula 1 in the second step of step three is regulated, and the second step of step three is:

[0169] Step 2, according to the liquid-solid ratio of 3:1, deionized water and the above-mentioned manganese hydroxide precipitation beating, add formula 1-B (15 times the total amount of calcium and magnesium) to the slurry, and then add to the slurry Feed carbon dioxide until the pH value of the slurry reaches 7, then stop the carbon dioxide feed, and filter immediately, thereby realizing the removal of calcium and magnesium in manganese hydroxide.

[0170] Other operations and parameters are the same as in Example 1.

[0171] The composition of the prepared battery-grade manganese sulfate solution is shown in Table 3.

[0172] Impurity requirements and the impurity content (ppm) of the present embodiment product in table 3 battery grade manganese sulfate

[0173] element ΣFe K Na Ca ...

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Abstract

The invention belongs to the field of smelting, and particularly relates to a method for preparing battery-grade manganese sulfate from manganese oxide ore, which comprises the following steps of: (1) leaching: carrying out first-stage leaching on manganese oxide ore, biomass and sulfuric acid, roasting leaching slag, mixing the roasted material and first-stage leaching liquid, carrying out second-stage leaching, and separating to obtain leaching liquid; (2) first-stage impurity removal: adding ferric sulfate, a manganese oxidizing agent and sulfide into the leachate to obtain first-stage impurity removal liquid; (3) second-stage impurity removal: carrying out manganese precipitation treatment on the first-stage impurity removal liquid to obtain a manganese hydroxide precipitate, dispersing the precipitate and a compound shown in the formula 1 in a solvent to obtain slurry, introducing carbon dioxide into the slurry, and carrying out second-stage impurity removal and solid-liquid separation to obtain impurity-removed manganese hydroxide; and (3) third-stage impurity removal: dissolving the impurity-removed manganese hydroxide with sulfuric acid, and then adding BaS and BaF2 to obtain a battery-grade manganese sulfate solution. The method disclosed by the invention is high in recovery rate and can be used for preparing high-quality battery-grade manganese sulfate.

Description

technical field [0001] The invention belongs to the technical field of hydrometallurgy, in particular to a method for preparing battery-grade manganese sulfate from manganese oxide ore. Background technique [0002] Battery-grade manganese sulfate is one of the main raw materials for the preparation of ternary cathode materials for lithium-ion batteries. It is usually required that the content of K, Na, Ca, and Mg in it is not higher than 50ppm, and the content of Fe, Cu, Zn, and Pb is not higher than 10oom. The content is not higher than 5ppm, the As content is less than 1ppm, and the F content is less than 700ppm; in addition, with the decline of subsidies for electric vehicles, battery material manufacturers are also being forced to continue to reduce costs. Therefore, the use of low-grade raw materials and the development of low-cost impurity removal technology are of great significance to battery-grade manganese sulfate manufacturers. At present, quite a lot of process...

Claims

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Application Information

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IPC IPC(8): C01G45/10
CPCC01G45/10C01G45/003Y02P10/20
Inventor 郝江楠黄琳黄远平周向清
Owner 湖南烯富环保科技有限公司
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