JPS6142769B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a method for treating manganese ore, and its purpose is to facilitate the excessive separation of solids in a slurry of manganese ore powder, and to substantially remove iron and aluminum from the solution from which the solids have been separated. The purpose of the present invention is to provide a method for obtaining a solution free of . Another object of the present invention is to use the solution from which the solids in the slurry have been separated as a raw material for producing electrolytic manganese metal, electrolytic manganese dioxide, etc. or as various industrial chemicals, and to The objective is to use it as a raw material for ferromanganese. Currently, the manganese salt solution used for electrolytic metal manganese, electrolytic manganese dioxide, etc. is made by adding acid such as sulfuric acid or hydrochloric acid to manganese ore that has been reduced and roasted in advance, and then converting the manganese content in the manganese ore into manganese sulfate or It is manufactured as a manganese salt solution such as manganese chloride. Conventionally, in the extraction process, in order to extract as much manganese as possible, the pH of the slurry is made strongly acidic at 2.0 or less, and the manganese extraction rate is set at 85% or more. However, if the pH during manganese extraction is set to 2.0 or less, not only the manganese in the manganese ore but also iron, aluminum, etc. will be extracted and dissolved into the solution at the same time. Therefore, conventionally, in order to remove impurities such as iron and aluminum, an alkaline component such as calcium carbonate is added to the solution to neutralize it, and the iron, aluminum, etc. are precipitated as hydroxide, which is then filtered to form solids. They are separated from each other. However, the hydroxide that precipitates in the above method is very fine and it is difficult to quickly filter it out even if a super-aid is used. A method of using reduced manganese ore as a neutralizing agent instead of calcium carbonate has also been proposed, but the neutralization is worse than that of calcium carbonate. Furthermore, when neutralizing with calcium carbonate, reduced manganese ore, etc., solid matter (hereinafter referred to as residue)
The disadvantage is that the total amount of filtrate increases, thus making filtering the residue more difficult. As mentioned above, the excessive deterioration of the residue also allows salts such as manganese sulfate to be contained in the residue, and it is difficult to remove manganese sulfate and the like from the residue even by washing several times. In this way, residues containing sulfate groups inevitably lead to an increase in sulfur in the raw material, and therefore such residues cannot be reused as raw materials for ferromanganese, and those containing manganese chloride are Such residue is exclusively discarded because it generates gas and not only pollutes the environment but also damages equipment on the furnace due to chlorine gas. Furthermore, when discarding, it is necessary to add calcium hydroxide, cement, etc. to prevent the elution of water-soluble manganese salts. The present invention solves the various drawbacks of the conventional methods described above by having the structure described in the claims, and provides a liquid that is easy to clean and does not substantially contain iron, aluminum, etc. At the same time, it was possible to obtain a method in which the solution can be used as a raw material for electrolytic manganese metal, electrolytic manganese dioxide, etc., or as various industrial chemicals, and the residue separated by filtration can be reused as a raw material for ferromanganese. Next, the relationship between PH and the dissolution rate of manganese, iron, aluminum, etc. will be explained using Experimental Example 1 by varying the PH during extraction. Experimental Example 1 Reduced manganese ore as shown in Table 1 was slurried by adding 2,500 g of the reduced manganese ore and 6 parts of water to 10 containers equipped with a stirrer, and adding 50% sulfuric acid.
After 1.5 hours, the temperature was maintained at 85° C. for 1.5 hours and filtered to determine the dissolution rate of manganese, iron, and aluminum in the solution, and the results shown in Table 2 were obtained.

【table】

[Table] As is clear from Table 2, the dissolution rate of manganese at PH3.0 is 82%, and at PH0.5 it is 90.5%.
The increase in the dissolution rate was small, whereas iron,
It is observed that the dissolution rate of aluminum is extremely small at pH 2.8 or higher, but rapidly increases at pH 2.5 or lower. Next, a state in which the slurry after extracting manganese is over-separated will be explained as Experimental Example 2. Experimental Example 2 The same raw materials and the same equipment as Experimental Example 1 were used for dissolution treatment at each pH value, and after adjusting the pH to 5.0 to 5.2 while stirring, the diameter
The residue was separated by vacuum suction using a 23 cm filter, and the residue was washed with 1.5 parts of water in three portions to obtain the results shown in Table 3. In addition, PH0.5~
If the pH is 2.5, add reduced manganese ore to adjust the pH to 5.0 to 5.2.
Adjust to.

【table】

[Table] As is clear from Table 3, the overspeed decreases significantly as the pH decreases below PH2.5, while the amount of over-separated residue increases as the pH decreases. It will be done. On the other hand, at pH 2.8 to 4.0, no significant changes were observed in the overspeed and amount of residue. Furthermore, the water content in the residue increases as the pH decreases below PH2.5, and the amount of water-soluble manganese and total sulfur in the residue also increases as the pH decreases below PH2.5. From the above results, when the pH is below 2.5, the iron and aluminum extracted into the solution become a gel-like precipitate by adjusting the pH to 5.0 to 5.2, and are separated as a residue. Since it is in the form of a gel, water and sulfate are trapped in it, so it is thought that cleaning cannot be performed sufficiently at pH 0.5 to 2.5, and that the overspeed is greatly reduced. On the other hand, when the pH is set to 2.8 to 4.0, almost no iron or aluminum is extracted into the solution, so there is no significant decrease in overspeed due to the gel-like precipitate mentioned above, and there is no residue. There is no problem of insufficient washing, and therefore the risk of manganese salt remaining in the residue is greatly reduced. Furthermore, as in the present invention, the pH of the slurry
When stirring while maintaining the pH at 2.8 to 4.0, the pH can be adjusted to 5.0 to 5.2 by simple stirring without adding any neutralizing agent such as calcium carbonate, so free sulfuric acid in the solution It is also possible to remove trace amounts of iron, aluminum, etc. extracted into the solution. In addition, in Experimental Example 2, the pH after stirring and holding is 5.0 to 5.2, but the pH varies from 4.0 to 4.0 depending on the distribution ratio of manganese between the manganese salt solution and the residue.
It can be adjusted as appropriate within the range of 6.0, and a small amount of reduced manganese ore may be added while stirring when adjusting the pH. As described above, the present invention can greatly improve the overspeed by maintaining the pH of the manganese ore slurry at 2.8 to 4.0 and stirring without adding any neutralizing agent. The resulting manganese salt solution has almost no extraction of iron and aluminum, and free sulfuric acid can also be removed.
The manganese salt solution can be used for the production of electrolytic manganese metal, electrolytic manganese dioxide, and as a raw material for various industrial chemicals, and the residue obtained by over-separation has sulfates, hydrochlorides, etc. removed. This residue can be reused as a raw material for ferromanganese, making use of unused resources and further reducing costs. Example 1 Reduced manganese ore powder 100 used in Experimental Example 1
Kg was put into a dissolution tank with an internal volume of 500 ml and equipped with a stirrer, and 240 ml of water was added to form a slurry. Next, add 150 kg of (1+1) sulfuric acid to the slurry's PH
I spent 1.5 hours adding it to keep it at about 3.0. After continuing stirring for 30 minutes, the residue is separated using a vacuum filter with a diameter of 60 cm, and the residue is washed with 40 g of water in three portions (this washing liquid will be used for the next slurry preparation). The overspeed in this case is
At 160/m ² ·Hr, over-operation was very easy. Through the above-mentioned over-separation, a 2.9 mol/manganese sulfate solution 272 and a 0.87 mol/manganese sulfate washing solution 110 were obtained. This is the manganese extraction rate
This corresponds to 78.8%. Also, almost no iron or aluminum is extracted in this case. In addition, the residue has a dry weight of 37.9 kg, a total manganese content of 31.5%, and a total sulfur content of 1.1%, which is used in the sintering process of the pretreatment process for ferromanganese production by adding 10% to the manganese ore. We obtained fluoromanganese that is comparable to conventional products. Example 2 10 kg of the same reduced manganese ore powder as in Example 1 was put into a dissolving tank with an internal volume of 60 mm and equipped with a stirrer, and 66 g of water was added to form a slurry. Next, add 31.9 kg of (1+1) hydrochloric acid to the pH of the slurry.
I spent 1.5 hours adding it to keep it between 3.0 and 3.5. Thereafter, stirring was continued for 30 minutes, followed by vacuum filtration through a Nutsuie filter with a diameter of 30 cm, and the residue was washed with water 152 times (the washing liquid was used for the next slurry preparation as in Example 1). The overspeed in this case is
150/ ^m2 ． It was very easy to over-operate with Hr. The manganese hydrochloride solution, washing solution and residue obtained above are shown in Table 4.

[Table] Note that the above residue can be fully used as a raw material for ferromanganese.

Claims (1)

[Claims] 1. Add manganese ore powder that has been reduced and roasted in advance to water to make a slurry, and adjust the pH of the slurry to 2.8~2.8.
After adding acid to maintain the pH within the range of 4.0, stir thoroughly until the pH of the slurry is between 4.0 and 6.0.
A method for processing manganese ore, characterized in that the solid matter in the slurry is then over-separated to obtain a manganese salt solution, and the solid matter is reused as a raw material for ferromanganese.