JPS58151437A - Treatment of manganese ore - Google Patents

Abstract

PURPOSE:To separate easily solid matter by filtration and to obtain an Mn salt soln. free from Fe and Al and the solid matter for ferromanganese by subjecting a slurry of Mn ore powder after reduction roasting to acid extraction at a specified pH and by carrying out solid-liq. separation by filtration. CONSTITUTION:Water is added to Mn ore powder after reduction roasting to prepare a slurry, sulfuric acid is charged so as to keep the slurry at 2.8-4.0pH, and the slurry is well agitated until the pH becomes 4.0-6.0. Solid matter in the slurry is then separated by filtration. Thus, an Mn salt soln. contg. practically no Fe and Al due to the pH and solid residue freed of sulfate radicals by washing because of the high filterability are obtd. The soln. can be utilized as a starting material for electrolytic metallic Mn, electrolytic MnO2, etc. or as various industrial chemicals, and the solid residue can be utilized as a starting material ferromanganese.

Description

[Detailed Description of the Invention] The present invention is a method for processing manganese ore, the purpose of which is to
Another object of the present invention is to provide a method that facilitates the filtration separation of solids in a slurry of manganese ore powder and obtains a solution containing substantially no iron or aluminum in the solution from which the solids have been separated. Another object of the invention is to use the solution from which the solids in the slurry have been separated as a raw material for manufacturing electrolytic metallurgical guns, electrolytic manganese dioxide, etc. or as various industrial chemicals, and to use the solids separated by filtration from the slurry as a ferrochemical. It is used as a raw material for manganese.

Currently, manganese salt solutions used for electrolytic manganese metal, electrolytic manganese dioxide, etc. are made by reducing and roasting manganese ore in advance. By adding acid such as sulfuric acid or hydrochloric acid, the manganese content in manganese ore is produced as a manganese salt solution such as manganese sulfate or manganese chloride.

Conventionally, in the extraction step, in order to extract as much manganese as possible, the slurry is made strongly acidic with -20 or less, and the manganese extraction rate is set at 85% or more.

However, if -20 or less during manganese extraction, not only manganese but also iron is extracted from manganese ore.

Aluminum etc. are also 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.

Precipitate hydroxide from aluminum etc. and filter it.
Separated with solid matter.

However, the hydroxide that precipitates in the above case is extremely fine and it is difficult to filter it quickly even if a filter aid is used.

Also, a method has been proposed in which reduced manganese ore is used as a neutralizing agent instead of calcium carbonate, but the filterability is poorer than that of calcium carbonate. Furthermore, when neutralizing with calcium carbonate, reduced manganese ore, etc., the total amount of solids (hereinafter referred to as residue) increases, making filtering the residue more difficult.

As mentioned above, the filterability of the residue deteriorates, and at the same time, it is difficult to remove manganese sulfate and the like from the residue even after washing several times, since it allows salts such as manganese sulfate to be contained in the residue. In this way, residues containing sulfur and acid 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 This produces chlorine gas, which not only pollutes the environment but also corrodes equipment on the furnace, so the residue is exclusively disposed of. 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 P liquid that is easy to filter and does not substantially contain iron, aluminum, etc. At the same time, the solution is mixed with electrolytic metal manganese,
We were able to obtain a method that can be used as a raw material for electrolytic manganese dioxide or various industrial chemicals, and in which the residue separated by filtration can be reused as a raw material for ferromanganese.

Next, by varying the − during extraction, − and manganese,
The relationship with the dissolution rate of iron, aluminum, etc. will be explained using Experimental Example 1.

Experimental Example 1 Reduced manganese ore as shown in Table 1 was prepared using a stirrer.
The reduced manganese ore 25009 and 6 tons of water were added to an O7 container to form a slurry, 50% sulfuric acid was added, the temperature was kept at 85°C for 1.5 hours, and then filtered to remove the manganese and iron in the solution. , the dissolution rate of aluminum was determined, and the results shown in Table 2 were obtained.

As is clear from Table 1 and Table 2, the dissolution rate of manganese at pf<5pf43.0 is 82%, and at pf10.5 it is 90.
At 5%, the dissolution rate increases by 1%), whereas the dissolution rate of iron and aluminum increases by -2.8 or more.
While it is slight, it is observed that it increases rapidly at pH 2.5 or lower.

Next, a description will be given as Experimental Example 2 of a condition in which the sura IJ- after extracting manganese is filtered and separated.

Experimental example 2 The same raw materials and the same equipment as experimental example 1 were melted at each value,
After adjusting the - to 5.0 to 52 while stirring, the diameter was 23CI.
The residue was filtered and separated by vacuum suction filtration using a No. In addition, when PHO is 5 to 25, reduced manganese ore is added to adjust it to -5.0 to 5.2.

As is clear from Table 3, the filtration rate significantly decreases with a decrease in pH below 2.5, while the amount of residual liquid after filtration increases as the pH decreases.

On the other hand, at pH 2,8~1+,0
No significant changes were observed in overspeed or residue amount.

In addition, the water content in the residue increases as the temperature decreases below pH 2.5, and the amount of water-soluble manganese and total sulfur in the residue also increases as the temperature decreases below pH 2.5. From the above results, in the case of p) 12.5 or less, it was extracted into the solution. By setting - to 5.0 to 5.2, iron and aluminum form a gel-like precipitate and are separated as a residue, but since the iron precipitate is gel-like, moisture and sulfate are trapped in this. Since pJ(0,5~2
．． It is considered that in case No. 5, washing could not be carried out sufficiently and the filtration rate was also significantly reduced.

On the other hand, when the pH is set to 0 from 28 to I+, almost no iron or aluminum is extracted into the solution, so
There is no significant decrease in filtration rate due to the gel-like precipitate as described above, and the residue is not washed insufficiently, so the possibility that manganese salt remains in the residue is greatly reduced.

Furthermore, as in the present invention, - of the slurry can be adjusted to 213 to I
When stirring while maintaining +, 0, it is possible to set it to -5.0 to 5.2 by a single stirring operation without adding any neutralizing agent such as calcium carbonate.
Free sulfuric acid in the solution and trace amounts of iron, aluminum, etc. extracted in the solution can also be removed. In addition, in Experimental Example 2, - after stirring and holding is 5, θ ~ 5.2, but p) can be adjusted as appropriate in the range of 14.0 to 6.0 depending on the distribution ratio of manganese between the manganese salt solution and the residual solution. It is also possible to add a small amount of reduced manganese ore while stirring during the adjustment.

As described above, the present invention has the advantage that the manganese ore slurry has -2
．． The filtration rate can be greatly improved by maintaining the 8 to I+, 0 and stirring without adding any neutralizing agent, and the manganese salt solution obtained by filtration has almost no extraction of iron or aluminum. Since free sulfuric acid can also be removed, the manganese salt solution can be used to produce electrolytic manganese metal, electrolytic manganese dioxide, and as a raw material for various industrial chemicals. .

Since hydrochloride and the like are removed, the residue can be reused as a raw material for ferromanganese, making it possible to utilize unused resources and further reduce costs.

Example 1 Reduced manganese ore powder 100119 used in Experimental Example 1
into a dissolution tank with an internal volume of 5001 and equipped with a stirrer,
21+Ot of water was added to form a slurry.

Next, 150"9 of (1+1) sulfuric acid was added over a period of 1.5 hours so that the - of the slurry was maintained at approximately 3.0.

Thereafter, stirring was continued for 30 minutes, and the residue was separated using a vacuum filter with a diameter of 60 CvA, and the residue was washed with water 1+O7 divided into three portions (this washing liquid was used for the next slurry preparation).

In this case, the filtration operation was very easy with a filtration speed of 16 ot, 7♂·Hr.

2. Due to the excess p mentioned above. ．． 9 mol/l of sulfuric acid,
Gungan solution 2721 and O, B 7 mo17'l (
11-ql of washing solution of D manganese sulfate was obtained. This corresponds to a manganese extraction rate of 78.8%. Also, almost no iron or aluminum is extracted in this case.

The dry weight of the residue is 37.9 kg, and the total manganese content is 31.5% and the total sulfur content is 1.1%. By blending and using it, we obtained colorless ferromanganese that was inferior to conventional products.

Example 2 The same reduced manganese ore powder 10J9 as in Example 1 was put into a dissolution tank with an internal volume of 60/m and equipped with a stirrer, and 6 tons of water was added to form a slurry.

Next K(1+1)[a! 31.9J9, slurry -
The mixture was poured over 1.5 hours to maintain a value of 5.0 to 3.5.After that, stirring was continued for 30 minutes, and vacuum filtration was carried out through a Nutsche with a diameter of 3Qc+m, and water 157 was divided into two portions. (The washing liquid will be used for the next slurry preparation as in Example 1.)

The filtration rate in this case was 1501/♂·Hr, and the filtration operation was very easy.

Manganese hydrochloride solution obtained above.

The washing solution and residue are as in 1st+i.

Table 1 Note that the above residue can be fully used as a raw material for ferromanganese.

Claims (1)

[Claims] Manganese ore powder that has been reduced and roasted in advance is added to water to make a slurry, and after adding acid to keep the - of the slurry in the range of 2.8 to 4.0, the - of the slurry becomes 4.
0 to 6.0, and then the solid matter in the slurry is separated by filtration to obtain a manganese salt solution, and the solid matter is reused as a raw material for ferromanganese. Ore processing methods.