KR870002076B1 - Manufacturing method of electrolysis metal mn from ferro mn slag - Google Patents

Abstract

In the method of selectively dissolving and separating Mn by applying the solution of (NH4)2SO4 or NH4Cl to pulverized Mn slag, the solution containing extracted Mn is controlled to an appropriate pH to be added with (NH4)2S and H2S to remove impurities and then electrolyze with addition of H2SeO4 and SO2 to obtain pure metal Mn. The direct application of (NH4)2SO4 to the pulverized Mn slag simplifies Mn extraction from the slag.

Description

Method for producing electrolytic metal manganese from Fero manganese slacks

The present invention uses manganese slack that is disposed of after decomposing manganese from manganese ore and extracts and separates manganese contained in this slack with a solution such as (NH ₄ ) ₂ SO ₄ or NH ₄ Cl and directly extracts the extract. The present invention relates to a method for producing electrolytic metal manganese from manganese slack by obtaining metal manganese by electrolysis.

In general, the manufacturing method of metal manganese is (1) heating and reducing manganese ore with an appropriate reducing agent to form manganese monoxide in an MnO state, which is dissolved in sulfuric acid to form manganese sulfate, or (2) SO ₃ gas in ore in manganese dioxide state. It has been developed by introducing manganese sulfate to add and ammonium sulfate separately added to the electrolysis.

(3) If the ore is present in the state of manganese carbonate, the ore can be dissolved directly in sulfuric acid to make manganese sulfate relatively easily. (4) The reduced manganese ore in (1) is added to carbonic acid by adding ammonium carbamate. You can also make manganese and make manganese sulfate by dissolving it in sulfuric acid in the same way. (4) Manganese carbonate can be made by adding ammonium carbamate to the manganese ore reduced in (1) above to make manganese sulfate. There is also.

However, the above method (1) has a drawback in that a reducing agent must be added separately. In the above method (2), a step of blowing SO ₃ gas must be involved, and the method of the above (3) method. Is difficult to process due to the generation of CO _{2. In} the method of the above (4), the defects and the four methods that are difficult to prepare (NH ₄ ) ₂ CO ₂ NH ₂ are both (NH ₄ ) ₂ SO ₄ and NH _4. Although there were drawbacks to add Cl separately, the present method has the advantage of easily separating and extracting manganese in slack by adding (NH ₄ ) ₂ SO ₄ NH ₄ Cl directly to manganese slack powder. It is difficult to find ore manganese raw materials that are currently in shortage worldwide.

In the present invention, since the manganese slacks are used at an annual rate of about 10,000 tons discarded in Korea, there is a great advantage in terms of utilization of manganese raw materials and economical manganese solution. Slags are generally separated into metals and slacks by hot melting with the addition of suitable fluxes and reducing agents in an electric furnace. As manganese slag also manganese ore sample flux with lime and as being added to the graphite, etc. as a reducing agent by-product in a hot melt state of the Mn (Ⅱ) condition part is not reduced to all-metal state of the manganese oxide in the sample flux and as SiO ₂ Together they form a complex mixture.

Manganese slack discarded in Korea contains a considerable amount of manganese, as shown in the following table.

TABLE 1

Table of Manganese Slacks

First, the manganese slack is crushed to about 200 to 250 mesh, and a certain amount of sample is taken and reacted with (NH ₄ ) ₂ SO ₄ or NH ₄ Cl solution, where (NH ₄ ) ₂ SO ₄ concentration, reaction temperature, reaction time, etc. As a result, the best conditions for selectively separating and extracting only manganese in slab are found.

TABLE 2

Effect of (NH ₄ ) and SO ₄ Concentration on Extraction

TABLE 3

Effect of Temperature on Extraction

TABLE 4

Influence of time on extraction

As shown in the above tables, as the (NH ₄ ) ₂ SO ₄ Mn extraction rate in the slack can be seen that more than 90% Mn extracted at a concentration of 6N, temperature 80 ℃, about 100 minutes.

In general, the extraction rate increases with increasing concentration of (NH ₄ ) ₂ SO ₄ , and the extraction rate increases with increasing temperature or reaction time. And the particle size of the sulfa also increases as the finer particles. The analysis table of (NH ₄ ) ₂ SO ₄ , MnSO _{4 complete} layer solution separated and extracted in this way is shown in the following table.

TABLE 5

Chemical Analysis Table of Extract

As shown in the table above, almost 90% or more of Mn, which cannot be separated and extracted with acids or other salts in general, has been extracted. In particular, more than 25% of acid-soluble silicic acid or calcium can be seen that only a small amount is dissolved. In order to purify the extracted solution by adding a little (NH ₄ ) ₂ SO ₄ to adjust the pH to 6.0 6.2, Al or a small amount of Fe dissolved in the solution is precipitated in the form of metal hydroxide (M (OH) ₃ ) again. At this time, the dissolved Si or Ca ions are also adsorbed, separated and precipitated. Then, a small amount of (NH ₄ ) ₄ S solution and activated carbon are added thereto, and the mixture is slowly stirred for about an hour to remove all traces of copper, zinc, nickel and cobalt. It is precipitated in the form of sulfide (MS) of the metal and is filtered out together with some carbon dissolved in the slag. At this time, the sulfur ions (S ⁼ ) remaining slightly in the solution also serves to increase the electrolytic efficiency during the later electrolysis. The analysis table of the purified solution is as follows.

TABLE 6

Analysis Table of Purified Solution

In order to deliver this solution, 40-50 g / l MnSO ₄ , 125-150 g / l (NH ₄ ) ₂ SO ₄ , 0.1 g / l SO ₂ and anode Anode) 10 ~ 20g / l MuSO ₄ , 25 ~ 40g / lH ₂ SO ₄ , 125 ~ 150g / l (NH ₄ ) ₂ SO ₄ , each was added to separate the concentration of the solution.

Lead electrode or graphite electrode mixed with 99% Pb and Ag 1% (using zinc electrolytic electrode) is melted on the anode electrode, and stainless steel plate or metal Ti is used on the cathode electrode. The plate was placed, and electrolysis was continued for 12 hours while maintaining a current density of 45 60 mA / cm 2 and an electrolytic voltage of about 5.0 V. At this time, the temperature was kept at room temperature.

In general, the higher the temperature, the lower the electrolytic efficiency, and the concentration of (NH ₄ ) ₂ SO ₄ was best at 125 150g / l. As the concentration increased, the current efficiency decreased.

In particular, the current density of 50 ㎃ / ㎠ was the best, and when the current density increased from 10 to 20.30.40, the electrolytic efficiency also increased, but the electrolytic efficiency rapidly decreased when it exceeds about 70 ㎃ / ㎠. Here, the pH of the solution was still kept at 6.0 7.0 0.1g / l, or (H) the SO ₂ to the cathode electrode _{2 SeO 4 0.03 (g / l} ) was added, so the degree was able to prevent precipitation of manganese while preventing oxidation It was possible to stabilize the solution.

The quality of the metal manganese thus delivered is shown in the table below.

TABLE 7

Analysis table of metal manganese

Example 1

(The extract is an example in which (NH ₄ ) ₂ SO ₄ is used and the anode pole is a lead electrode.)

The solution extracted and purified as described above from the slag was electrolyzed in the following composition.

Current density (㎃ / ㎠) 45

Cathode pH 6.2

Wax Composition Pb 99% Ag 1%

Cathode Composition Stainless Steel Plate # 316

Electrolytic Voltage (V) 5.0

Example 2

(Same as Example 1, but the graphite electrode is used for the anode and the metal titanium is used for the cathode.)

Current density (㎃ / ㎠) 60

Cathode pH 7.0

Anode composition graphite electrode

Cathode composition titanium metal electrode

Electrolytic Voltage (V) 5.2

Example 3

(Same as Example 1, but using NH ₄ Cl as an extract, and H ₂ SeO ₄ as an additive.)

The same result can be obtained by using NH ₄ Cl solution instead of (NH ₄ ) ₂ SO ₄ . However, NH ₄ HO ₃ was well extracted with Mn but the electrolysis result was not good.

Current density (㎃ / ㎠) 60

Cathode pH 6.0

Anode composition graphite electrode

Cathode Composition Stainless Steel Plate # 316

Electrolytic Voltage (V) 5.0

Electrolytic Temperature (℃) 40

Claims (1)

A micronized manganese slag (NH ₄₎ there as the ₂ SO ₄ solution or, NH ₄ Cl solution, a suitable amount of added separate only dissolved selection of manganese, (NH _{4) 2} separated and extracted with a solution of solution and NH ₄ Cl of SO ₄ Electrolyte from the manganese slack characterized by obtaining a pure manganese metal by adjusting the pH of the prepared product and adding impurities to it (NH ₄ ) ₂ S and H ₂ S to remove impurities, and adding it to H ₂ SeO ₄ and SO ₂ . Method of manufacturing metal manganese.