JPH083659A - Method for producing raw material for Mn alloy - Google Patents

Abstract

(57) [Summary] [Objective] To provide a method for producing a Mn alloy while effectively utilizing Mn resources. [Constitution] Manganese nodule is melted in a reducing atmosphere in two steps to form a slag having a low content of Cu, Ni, Co and P and a high Mn, and the slag is used as a raw material for producing an Mn alloy.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a raw material for Mn alloy from manganese nodules.

[0002]

2. Description of the Related Art Manganese nodules are widely distributed in the deep sea floor, contain Mn, Ni, Co, Cu, etc., and have a high content of useful metals. ing.

Many researches have been made so far on the treatment method of this manganese nodule, and several treatment methods have been proposed.

However, Ni, a manganese nodule, is mainly studied as a target to be recovered.
Mn, which is the metal with the highest content of Co and Cu
Has been rarely attempted.

The reason for this is that the Mn content in manganese nodules is considerably lower than that of ordinary Mn ores, and further, in the case of producing an Fe-Mn alloy, which is the main use of Mn. , Ni, Co, and Cu as impurities reduce the quality of the alloy, and P exceeds the standard value of the alloy.

Therefore, manganese nodules are replaced with Ni and Co.
When only Cu and Cu are limited to the target feedstock, Mn, which accounts for the majority of the components, is destined to be discarded as slag or residue.

Under such circumstances, if Mn in the manganese nodule is to be recovered and used, Ni, Co, Cu and P in the manganese alloy raw material (slag) are to be recovered.
Need to be reduced.

In this case, if manganese nodules are weakly reduced, Ni, Co, and Cu are likely to enter the slag, and thus the manganese alloy raw material. Conversely, if they are strongly reduced, Mn and F are reduced.
Since e enters the metal and Mn and Fe in the slag (manganese alloy raw material) are reduced, this adjustment is extremely difficult.

That is, when manganese nodules are simply strongly reduced, almost all Fe and a part of Mn contained in the manganese nodules are metallized with the metallization of valuable metals.

As a result, in the final production of manganese alloy, the recovery rate of Mn will decrease.

[0011]

DISCLOSURE OF THE INVENTION The present invention improves the conventional situation, and when the slag produced in the reduction step of manganese nodule is used as a raw material for the Mn alloy, the Mn in the raw material is
It is an object of the present invention to provide a method of increasing the content and reducing Ni, Co and P.

[0012]

Means for Solving the Problems As a result of earnest research and development aimed at solving the above problems, the present inventors have
The manganese nodule is reduced in two stages to reduce 1/2 to 1/3 of the iron content in the slag produced in the first-stage reduction process, and the iron component is added to the first-stage reduced slag in the second-stage reduction process. The inventors have found that the problems can be solved by doing so and have disclosed the present invention.

That is, according to the present invention, manganese nodule is melted in a reducing atmosphere to reduce Fe by 1/2 to 1/3 to form a slag having a low content of Cu, Ni, Co and P. Then, a second stage reduction treatment is performed to provide a manufacturing method using the slag as a raw material for Mn alloy.

Further, according to the present invention, the contents of Cu, Ni, Co and P in the target Mn raw material slag are Cu:
0.02% or less, Ni: 0.02% or less, Co: 0.0
A method for producing a slag adjusted to 2% or less and P0.05% or less and using this slag as a raw material for producing a Mn alloy will be presented.

Further, in the method for producing the Mn alloy raw material slag according to the present invention, the reduction treatment is preferably a melting treatment by adding coke or a melting treatment by a carbon electrode furnace, and the addition amount of C to the slag is 5% by weight. ~ 2
It is more preferably 0%.

As described above, manganese nodules are melted in a reducing atmosphere in two steps to form Ni, Co, Cu.
Is preferably metallized and separated and removed, and the slag remaining afterwards is used as the Mn raw material.

[0017]

[Function] By the first-stage reduction melting, a slag containing a part of nickel, cobalt, copper, and iron reduced from manganese nodules is produced, and in the second-stage reduction melting,
By adding an iron source commensurate with the reduced amount of iron, a manganese alloy raw material (slag) having low nickel, cobalt, copper and phosphorus can be obtained.

That is, according to the present invention, manganese nodules are melted in a reducing atmosphere in two steps to form Cu and N.
Since a slag having a low content of i, Co and P is made, and the slag has a high Mn content and contains sufficient Fe,
If the slag is used as a raw material for producing a Mn alloy, M
The purity of the n alloy increases.

In the first-stage reduction step, Ni, Co, Cu and Fe are reduced and metallized under the condition that 1/3 to 1/2 of the iron component contained in manganese nodule is reduced, Ni, Co, Cu in slag is reduced. As a result, in the second-stage reduction step, Mn: 20-40 by weight%
%, Fe: 1 to 5%, Cu: 0.01 to 0.20%, N
i: 0.01 to 0.20%, Co: 0.05% or less, P
A slag containing 0.07 to 0.5% is used as a raw material, 3 to 7% by weight of iron is added to the slag, and the slag is added. Get to push further metallization.

Here, when the iron content to be supplemented is less than 3% by weight, the amount of P remaining in the slag increases, and conversely, when it exceeds 7% by weight, the degree of purity improvement of the Mn alloy is saturated. On the other hand, since the amount of raw materials to be processed increases, the manufacturing cost increases.

Further, the insertion raw material obtained here is melted in a reducing atmosphere, and Cu, Ni, and
The contents of Co and P are Cu: 0.02% or less, Ni: 0.02% or less, Co: 0.02% or less, P, respectively.
M with slag adjusted to be 0.05% or less
It is used as a raw material for the production of n-alloys, thereby increasing the utility value of materials that have been conventionally disposed of.

Further, in the present invention, the reduction treatment is carried out by melting treatment by addition of coke or melting treatment by a carbon electrode furnace, and the addition amount of C to the slag is 5 to 20% by weight. By carrying out the treatment, the Mn content in the raw material can be increased, and as a result, a high-purity Mn alloy can be obtained.

In this case, if the amount of C added to the slag is less than 5% by weight and is out of the range, reduction of valuable metals such as Cu does not proceed, and the amount of C added becomes less than 5%. If the amount of Mn exceeds 20%, the reduction of Mn into the metal will proceed significantly, the Mn content in the raw material will be extremely small, and the Mn recovery will not be achieved.

[0024]

EXAMPLES Examples of the present invention will be described in detail below.

[Example 1] As shown in Table 1, Ni: 1.58%, Co: 0.19%, C in% by weight, respectively.
u: 1.21%, Fe: 4.72%, Mn: 32.2%
And P: 0.15% manganese nodule 2 kg
, Coke was added so that the coke ratio was 9% by weight, and 150 g of silica was inserted as a solvent into an alumina crucible, and pre-reduction was performed by pre-heating at 900 ° C. for 2 hours in an electric furnace. Further, it was held at 1400 ° C. for 2 hours. As a result, the composition of each of the obtained slags was Ni: 0.02%, Co:
0.01% or less, Cu: 0.05%, Fe: 2.47
%, Mn: 31.7% and P: 0.2%, the composition of the metal in% by weight, respectively, Ni: 30.2%, C
o: 3.63%, Cu: 22.9%, Fe: 40.5
%, Mn: 0.44% and P: 0.3%.

In this case, the reason that the Mn content in the slag was slightly decreased was that the slag amount was increased by the addition of the solvent, and there was almost no loss as a metal.

By this reduction treatment, almost half of the iron was metallized. In the slag, 0.0 with the remaining Fe
Since Cu and P that exceed 2% are present, they cannot be used as raw materials for the Mn alloy as they are.

Therefore, 200 g of crushed slag obtained by crushing this slag was used as a Mn raw material, 8 g of electrolytic iron as an iron source and 16 g of coke for a reducing agent were added to the slag crushed piece, and the slag was put into an alumina crucible to obtain electricity. Perform preliminary reduction by preheating at 900 ° C for 2 hours in the furnace, then 1400 ° C
After holding for 2 hours, it was cooled to room temperature in the furnace.

Then, the crucible cooled in the furnace was crushed, and 180 g of slag and 12.6 g of metal were taken out separately.

The composition of the slags obtained in this case is, respectively, in weight%, Ni: 0.01% or less, Co: 0.01%.
Below, Cu: 0.01% or less, Fe: 0.61%, M
n: 31.4%, P: 0.02% or less and S: 0.0
5% or less, the composition of the metal in each weight%, N
i: 0.10%, Co: 0.04%, Cu: 0.65
%, Fe: 92.1%, Mn: 0.90% and P:
It was 2.9%.

The slag thus obtained was used as a raw material for the Mn alloy, but no inconvenience was found.

[0032]

[Table 1]

Example 2 As a result of melting in the same manner as in Example 1 except that 14 g of iron oxide was used as an iron source and 36 g of reducing coke was used, 9.8 g of metal and 185 g of metal were obtained.
And the composition of the slag in this case is, as shown in Table 2, in weight%, Ni: 0.01% or less, Co: 0.01% or less, Cu: 0.01% or less. , F
e: 0.48%, Mn: 29.6%, P: 0.02% or less and S: 0.05% or less, and the composition of the metal in% by weight is respectively Ni: 0.17%, Co. : 0.06
%, Cu: 0.85%, Fe: 95.2%, Mn: 0.
24% and P: 3.7%.

No inconvenience was found when the slag thus obtained was used as a raw material for the Mn alloy.

Here, although the Mn quality in the slag seems to have decreased, this is because the alumina is dissolved and mixed in from the crucible, and the loss amount of metal loss due to the metal reduction treatment is almost recognized. There was no

[0036]

[Table 2]

As described above, the second stage reduction step of adding the iron component to the slag in the first stage reduction step of reducing 1/3 to 1/2 of the iron contained in the manganese nodule to perform reduction treatment Raw materials (slag) for producing the Mn alloy were readily available.

When the strength of the first-stage reduction step was made stronger than that in Example 1, the Mn content of the first-stage reduced final slag became much lower than that of manganese nodule.

In the above examples, electrolytic iron or iron oxide was used, but as long as it does not contain polluting elements,
It goes without saying that there is no problem in terms of iron content, whether it is low-grade iron scrap or iron ore.

Further, although Cu, Co, Ni and P are targeted as the elements coexisting with Mn in the examples, any element nobler than Mn can be sufficiently applied.

[0041]

When the present invention is carried out, most of Ni, Co, Cu and P in the Mn raw material are transferred to the metal, and the remaining slag is used as a raw material for producing the Mn alloy. You can definitely use it.

Furthermore, if this slag is subjected to a reduction treatment, it becomes possible to manufacture a high-purity Mn alloy in which Ni, Co, Cu, and P are extremely low.

Then, while deliberately collecting it from the deep sea, the manganese nodule was melted in a reducing atmosphere, and N
It is possible to effectively use Mn raw materials that have not been conventionally used and are abandoned as they are, such as slag left after metallizing i, Co, and Cu for separation and removal, as resources for Mn alloys. Became.

Claims (4)

[Claims] 1. The reduction refining of manganese nodule is carried out by dividing it into a first-stage reduction process and a second-stage reduction process, and in the first-stage reduction process, 1/2 to 1/3 of the iron content in the produced slag is removed. Manganese nodules are melted and reduced to reduce
The slag having a low content of Cu, Ni, Co, Fe and P is produced by subjecting the final slag in the first reduction step supplemented with iron to a melt reduction treatment in the second reduction step. A method for producing a raw material for Mn alloy. 2. In the first reduction step, Mn:% by weight,
20-40%, Fe: 1-5%, Cu: 0.01-0.
20%, Ni: 0.01 to 0.20%, Co: 0.05
% Or less, making slag having P0.07-0.5%,
Iron is added to the slag in an amount of 3 to 7% by weight and melted in a reducing atmosphere, and the contents of Cu, Ni, Co and P in the slag are Cu: 0.02% or less and N, respectively.
i: 0.02% or less, Co: 0.02% or less, P0.0
Adjusted to be 5% or less, and with this slag, Mn
The raw material for alloy production, The manufacturing method of the raw material for Mn alloys of Claim 1 characterized by the above-mentioned. 3. The reduction treatment is a melting treatment by addition of coke or a melting treatment by a carbon electrode furnace, and the addition amount of C to the slag is 5 to 20% by weight. The manufacturing method described in. 4. The first-stage reduction process and the second-stage reduction process, wherein the preliminary reduction is performed at a temperature of 800 ° C. to 1000 ° C., and then the reduction is performed at a temperature of 1300 ° C. to 1500 ° C. The manufacturing method according to any one of 1 to 3.