JP4816897B2 - Electrolytic extraction method of metal manganese and high purity metal manganese - Google Patents

Description

The present invention relates to a method for electrowinning metallic manganese and a high-purity metallic manganese obtained by this method. More specifically, the present invention relates to an electrolytic collection method capable of obtaining high-purity metallic manganese by preparing an electrolytic solution with few impurities, and the high-purity metallic manganese.

In general Mn electrowinning (sulfuric acid bath electrolysis), first, a trivalent iron ion is obtained by oxidizing a divalent iron ion by adding an oxidizing agent such as manganese dioxide to an electrolytic solution made of a manganese sulfate solution. In addition, an alkaline substance such as ammonia is added to remove trivalent iron ions as a hydroxide precipitate. At the same time, As and Si are also hydrolyzed to form hydroxide precipitates, which are removed together with iron.

On the other hand, Co, Ni, Cu, and Pb, which are noble metals than Mn, are not precipitated by the above method and remain in the electrolytic solution. Therefore, a sulfide precipitant such as sodium hydrosulfide or ammonium sulfide is added to the electrolytic solution. And removed as a sulfide precipitate. However, in the liquid from which the metal impurities have been removed, colloidal sulfur, fine powder, and sulfide precipitates due to the added sulfide precipitant exist, and in order to remove this, iron is further added by adding trivalent iron. There is a problem that the liquid purification process is very long because it is coprecipitated with the hydroxide and removed.

Moreover, about the electrowinning using a chloride bath, the method of using an ion exchange method as a liquid-cleaning method of Mn electrolyte solution is known (patent document 1). However, in the ion exchange method, the amount of ion exchange is affected by the concentration of impurity ions in the liquid. When the concentration is low, the amount of ions exchanged per unit resin amount is very small and the efficiency is poor. Moreover, since the amount of liquid flow is limited by the amount of ion exchange resin, it takes time to clean the liquid. Furthermore, there is a problem that it is necessary to regenerate the ion exchange resin and it takes time and effort for maintenance.
JP 2002-285373 A

The present invention solves the above-mentioned problems in the conventional electrowinning of metallic manganese, and in the electrowinning using a hydrochloric acid bath, it is possible to efficiently remove impurities from the liquid to prepare an electrolyte with less impurities, and to achieve high purity. An electrowinning method capable of obtaining a high-purity manganese metal is provided.

The present invention relates to a method for electrolytic collection of metallic manganese having the following configuration, and high-purity metallic manganese.
[1] Manganese hydrochloric acid solution in which manganese manganese is dissolved in hydrochloric acid to form a manganese hydroxide precipitate is formed. After the undissolved manganese hydrochloric acid solution is filtered, an oxidizing agent is added and neutralized. A method for electrolytically collecting metallic manganese, comprising using an electrolytic solution prepared by filtering a precipitate formed and adding a buffer.
[2] In the method for electrowinning metal manganese according to [1 ] above, a manganese hydrochloric acid solution in which manganese hydroxide precipitate is formed is dissolved by adding metal manganese to a solution obtained by dissolving metal manganese in hydrochloric acid. a solution obtained by, undissolved is a hydroxide precipitate of undissolved manganese metal and manganese, after filtering the undissolved, weakly acidic to medium by adding hydrogen peroxide and aqueous ammonia A method for electrolytically collecting metallic manganese, comprising using an electrolytic solution prepared by further filtering a precipitate generated under a neutral liquid and adding a buffer to the filtrate .
[3] Metallic manganese obtained by the electrolytic collection method of [1] or [2] above, and each of the impurity concentrations of Al, Cr, Zn, Cu, Fe, Pb, Co, and Si is less than 1 ppm. High-purity metallic manganese in which both Mg and Ca are less than 5 ppm.

The electrolytic collection method of the present invention is a manganese hydrochloric acid solution in which manganese manganese is dissolved in hydrochloric acid to form a manganese hydroxide precipitate. In this manganese hydroxide precipitate, As, Co, Ni, Cu, Zn, etc. Is taken in and coprecipitated, so that most impurities contained in the electrolyte are removed. In addition, an oxidizing agent is added to oxidize Fe, Pb, etc. in the electrolyte, and precipitates are formed from weakly acidic to neutral, and these precipitates are removed by filtration separation along with manganese hydroxide precipitation. As, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Zn, Si, etc., which are impurities contained in ordinary metal Mn and are noble than Mn, are reduced below the detection limit. Is done.

Therefore, according to the electrowinning method of the present invention, high-purity manganese metal can be obtained. Specifically, for example, each impurity concentration of Al, Cr, Zn, Cu, Fe, Pb, Co, and Si is any Is less than 1 ppm, and high-purity metallic manganese in which both Mg and Ca are less than 5 ppm can be obtained.

Hereinafter, the present invention will be specifically described together with examples.
In the production method of the present invention, manganese manganese is dissolved in hydrochloric acid to form a manganese hydrochloric acid solution in which manganese hydroxide precipitates are formed . After the undissolved material of the manganese hydrochloric acid solution is filtered , an oxidizing agent is added. In addition, a method for electrolytically collecting metal manganese is characterized by using an electrolytic solution prepared by filtering a precipitate produced by neutralization together with adding a buffering agent. FIG. 1 shows a schematic process of the electrolytic collection method of the present invention.

In the electrowinning method of the present invention, preferably, metal manganese is further added to a hydrochloric acid solution of metal manganese, hydrogen peroxide and aqueous ammonia are added to the solution obtained by filtering undissolved matter, and the mixture is weakly acidic or neutral. This is a method for electrolytic collection of metallic manganese using an electrolytic solution prepared by filtering a precipitate produced under the liquid condition of and adding a buffering agent.

Preparation of manganese hydrochloric acid solution in which metal manganese is dissolved in hydrochloric acid to form manganese hydroxide precipitate is prepared by , for example, dissolving metal manganese in hydrochloric acid and adding metal manganese to dissolve manganese to oxidize. A hydrochloric acid solution having a reduction potential (vs. AgCl) of -1.2 V to -0.5 V, preferably around -1.1 V may be prepared. Manganese forms a hydroxide precipitate in this hydrochloric acid solution, and this precipitate contains undissolved metallic manganese. Impurities such as As, Co, Ni, Cu, and Zn contained in the metal manganese are eluted in the liquid and taken into the manganese hydroxide precipitate to co-precipitate. These undissolved substances can be separated by filtration to obtain a hydrochloric acid manganese solution with few impurities [first stage precipitation step].

Furthermore, an oxidizing agent such as hydrogen peroxide is added to the hydrochloric acid manganese solution to oxidize Fe, Pb, etc. remaining in the solution, and further neutralized by adding ammonia water to weaken the liquidity. Adjust to acidity or neutrality to produce hydroxide precipitates such as Fe and Pb. Mn remaining in the liquid becomes a hydroxide precipitate. The timing for adding the oxidizing agent may be before the liquidity adjustment or after the adjustment. The liquidity may be adjusted to be weakly acidic to neutral, specifically, for example, pH 5.0 to 7.0, preferably pH 6.0 to 6.5. By filtering and separating these precipitates, a hydrochloric acid manganese solution with fewer impurities can be obtained [second stage precipitation step].

The precipitate is filtered and separated, and a buffer is added to the filtrate to prepare a manganese electrolyte. As the buffering agent, ammonium chloride or the like is used. Using this hydrochloric acid electrolytic solution, high-purity metallic manganese can be obtained by electrowinning. Electrolytic collection may be performed under normal conditions.

30 g of metal manganese was dissolved in 100 ml of hydrochloric acid and 400 ml of water. Further, 5 g of metal manganese was added to this primary solution to form an excessive solution, and the oxidation-reduction potential was set to -1.1 V, and then undissolved metal manganese and undissolved material in the solution were filtered. After 1.5 ml of hydrogen peroxide was added to this solution to oxidize iron and lead in the solution, ammonia water was further added to adjust the pH of the solution to 6.5, and the resulting precipitate was filtered. Removed.
After adding 50 g of ammonium chloride as a buffering agent to this filtrate (pH adjusting solution), it was charged in an electrolytic cell, electrolyzed at a cathode current density of 400 A / m ² using a stainless steel plate for the cathode, graphite for the anode. This gave 35 g of metal manganese. In addition, aqueous ammonia was added during the electrolysis to maintain the pH of the electrolyte at 6.2.
Table 1 summarizes the impurity content of the raw material manganese metal, the solution in each step, and electrolytic metal manganese. As shown in Table 1, high purity metal manganese having a grade of 5N or higher was obtained by this method.

40 g of metal manganese was dissolved in 100 ml of reagent grade hydrochloric acid and 420 ml of water at room temperature. Undissolved metal manganese coexisting in the solution and the produced manganese oxide precipitate were filtered and separated to obtain 500 ml of manganese chloride aqueous solution. The pH of the solution was 6.8, and the redox potential was −1.12V. After adding 40 g of ammonium chloride as a buffering agent to this manganese chloride aqueous solution (Mn oxide filtrate), it was charged into an electrolytic cell, a stainless plate was used for the cathode, graphite was used for the anode, and a cathode current density of 200 A / Electrolysis was performed at m ² to obtain 20 g of metal manganese. In addition, aqueous ammonia was added during the electrolysis to maintain the pH of the electrolyte at 6.2. The analytical values for each step are shown in Table 2.

Electrolysis was conducted in the same manner as in Example 2 except that the manganese post-electrolysis solution was used and metal manganese was dissolved. The results of analysis of the dissolved solution and the obtained metal manganese are shown in Table 3.

Schematic process diagram of the electrolytic collection method of the present invention

Claims (3)

Metal manganese was dissolved in hydrochloric acid to form a manganese hydrochloric acid solution in which a manganese hydroxide precipitate was formed. After the undissolved manganese manganese solution was filtered, an oxidizing agent was added and neutralized to produce A method for electrolytically collecting metallic manganese, comprising using an electrolytic solution prepared by filtering a precipitate and adding a buffering agent. 2. The method for electrowinning metal manganese according to claim 1, wherein a manganese hydrochloric acid solution in which manganese hydroxide precipitate is formed is obtained by further dissolving metal manganese in a solution obtained by dissolving metal manganese in hydrochloric acid. , and the undissolved is a hydroxide precipitate of undissolved manganese metal and manganese, after filtering the undissolved, hydrogen peroxide and aqueous ammonia was added weakly acidic to humoral neutral A method for electrolytically collecting metallic manganese, comprising using an electrolytic solution prepared by further filtering the precipitate generated below and adding a buffer to the filtrate . 3. Manganese obtained by the electrowinning method according to claim 1 or claim 2, wherein each impurity concentration of Al, Cr, Zn, Cu, Fe, Pb, Co, and Si is less than 1 ppm, and Mg, Ca Is a high-purity manganese metal that is less than 5 ppm.

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