TW201527541A - Method for manufacturing high purity manganese and high purity manganese - Google Patents

Abstract

The present invention relates to a method for manufacturing high purity Mn, the method being characterized in that: a Mn starting material is placed in a magnesia crucible and is melted at a melting temperature of 1240-1400 DEG C using a vacuum induction melting furnace (VIM furnace) under an inert atmosphere of 500 Torr or less; calcium is added in a range of 0.5-2.0% of the Mn weight to perform de-oxygenation and de-sulfurization; after completion of the de-oxygenation and de-sulfurization, an ingot is manufactured by pouring into an iron mold; then said Mn ingot is loaded in a scull melting furnace, the pressure is reduced to 10-5 Torr or less using a vacuum pump, and heating is started; and after the melted state is maintained for 10-60 minutes, the melting reaction is completed to obtain high purity Mn. The present invention provides a method for manufacturing high purity metal Mn from commercially available electrolytic Mn. In particular, the present invention addresses the problem of obtaining high purity metal Mn with low amounts of impurities such as B, Mg, Al and Si.

Description

Method for producing high-purity manganese and high-purity manganese

The present invention relates to a high-purity manganese (Mn) manufactured from commercially available electrolytic manganese (Mn) and a method for producing the same.

The method for producing manganese metal commercially available is an electrolytic method using an ammonium sulfate electrolytic bath, and the commercially available electrolytic manganese obtained by the method contains sulfur (S) of about 100 to 3,000 ppm and also contains hundreds of carbon (C). Ppm. It also contains hundreds of ppm of chlorine (Cl) and contains about several thousand ppm of oxygen (O) due to electrodeposition from aqueous solution.

As a method of removing S and O from the foregoing electrolytic manganese, a sublimation purification method is well known in the prior art. However, the sublimation purification method has the following disadvantages: the apparatus is very expensive and the yield is very poor. In addition, even if S and O can be reduced in the sublimation purification method, it is contaminated by the heater material and the condenser material of the sublimation purification device. Therefore, the manganese metal obtained by the purification method may be unsuitable as an electronic component. The problem of using raw materials.

As a prior art, Patent Document 1 discloses a method of removing sulfur in metal manganese by adding manganese oxides such as MnO, Mn ₃ O ₄ , and MnO ₂ and/or melting temperature of metal manganese. For the Mn oxide, for example, Mn carbonate or the like, the metal Mn to which the Mn compound is added is melted in an inactive environment, and is preferably kept in a molten state for 30 to 60 minutes to have a sulfur content of 0.002%.

However, in this document 1, for oxygen (O), nitrogen (N), carbon (C), chlorine (Cl) The content is not recorded at all, and the problems caused by the inclusion of these have not been solved.

Patent Document 2 listed below discloses a method for electrolytically refining manganese metal, which is characterized in that an electrolytic solution prepared by dissolving high-purity manganese metal in hydrochloric acid, filtering undissolved matter, and obtaining a solution, The solution is neutralized by adding an oxidizing agent, and the resulting precipitate is filtered, and a buffer is added, and a method of electrolytically refining manganese metal using the following electrolytic solution is described. Preferably, metal manganese is further added to the dissolved solution of manganese metal. The undissolved matter is filtered off to obtain a solution, and hydrogen peroxide and ammonia water are added to the solution, and a precipitate formed under a weakly acidic or neutral liquid property is filtered off, and a buffer is added to prepare an electrolytic solution.

However, in this document 2, although the description of reducing the sulfur of high-purity manganese to 1 ppm has been described, the contents of oxygen (O), nitrogen (N), carbon (C), and chlorine (Cl) are not described at all, and The problems caused by the problem have not been resolved.

Patent Document 3 listed below discloses a method for producing high-purity manganese, which is described by applying an ion exchange purification method in which a chelating resin is used in an aqueous solution of manganese chloride, and then purifying the aqueous solution of manganese chloride by electrolytic refining. A method of purifying. There is a description that the dry method obtains high purity from solid phase manganese by a vacuum sublimation purification method in which manganese vapor obtained by sublimation of solid phase manganese is selectively condensed and vapor-deposited in a cooling portion by vapor pressure difference. manganese.

Further, in this document 3, the total concentration of sulfur (S), oxygen (O), nitrogen (N), and carbon (C) is 10 ppm or less.

However, in this document 3, there is no description of the chlorine (Cl) content which is harmful to the manufacture of semiconductor parts. Since manganese chloride is used as a raw material, it may contain a high concentration of chlorine and is problematic.

Patent Document 4 listed below discloses a method for producing a low-oxygen manganese material, which is described as follows: inductive shell melting of a manganese raw material in an inert gas atmosphere (skull) Melting), a manganese material having a reduced oxygen amount of less than 100 ppm is obtained, and the manganese raw material is acid-cleaned before induction shell melting, since oxygen can be further reduced, which is preferable. However, although this document 4 describes the reduction of oxygen (O), sulfur (S), and nitrogen (N) in high-purity manganese, the content of other impurities is not described at all, and it is caused by such a content. The problem has not been resolved.

Patent Document 5 listed below discloses a manganese alloy material for a magnetic material, a manganese alloy sputtering target, and a magnetic thin film, and has an oxygen content of 500 ppm or less and a sulfur content of 100 ppm or less, preferably further containing impurities (manganese and The content of the elements other than the alloy component is 1000 ppm or less in total.

Further, in this document, there is described a method in which a high-purification method is carried out by vacuum distillation after preliminary melting, and this method is carried out by adding Ca, Mg, La or the like as a deoxidizing and desulfurizing agent to a commercially available electrolytic Mn. The frequency is melted, thereby removing oxygen (O) and sulfur (S).

In the above manganese raw material, in Example 3, there is described the following: a deoxidizing and desulfurizing agent is added for high-frequency melting to have an oxygen content of 50 ppm and a sulfur content of 10 ppm (Table 3 of Patent Document 5), and in Examples 7 has the following description: vacuum distillation is carried out after preliminary melting to have an oxygen content of 30 ppm and a sulfur content of 10 ppm (Table 7 of Patent Document 5). Further, in these examples, it contains about 10 to 20 ppm of Si and about 10 to 30 ppm of Pb.

However, the purity of manganese produced in the following Patent Document 5 is 3N, and the high-purity manganese obtained by the present invention cannot be obtained. Further, in the third embodiment of the following Patent Document 5, since the deoxidation and the desulfurizing agent are added to perform high-frequency melting, there is a problem that the deoxidizing agent and the desulfurizing agent are mixed into the manganese to lower the purity, and the problem is the same as in the seventh embodiment. In other cases, since vacuum distillation is performed after the preliminary melting, 99% or more of the dissolved manganese is volatilized, so that there is a problem that the manufacturing cost is high.

Patent Document 6 listed below discloses a method for producing a high-purity manganese material and a high-purity manganese material for film formation. The following description is given: In this case, the crude manganese is preliminarily melted at 1,250 to 1,500 ° C, and then vacuum distilled at 1100 to 1500 ° C to obtain a high-purity manganese material. It is preferred that the degree of vacuum in vacuum distillation is 5 × 10 ^-5 to 10 Torr.

The high-purity manganese obtained by this has a total impurity content of 100 ppm or less, oxygen (O): 200 ppm or less, nitrogen (N): 50 ppm or less, sulfur (S): 50 ppm or less, and carbon (C): 100 ppm or less. Further, in Example 2 (Table 2), an example in which oxygen is 30 ppm and other elements are less than 10 ppm is described. However, in this case, the degree of impurities does not reach the target level.

Further, Patent Document 7 listed below discloses a sputtering target composed of a high-purity manganese alloy, and Patent Document 8 describes a method for recovering manganese using sulfuric acid, and Patent Document 9 describes a method for heating manganese oxide. A method of reducing manganese metal, but there is no relevant description of desulfurization.

Therefore, the inventors of the present invention have proposed a production method in which a manganese raw material is leached by an acid, and the residue is filtered by a filter, and the filtered liquid is used on the cathode side during electrolysis, and the electrolytic manganese is removed. Gas treatment, the content of Cl in the electrolytic manganese is less than 100 ppm, further degassing the electrolytic manganese raw material, and melting in an inactive environment, thereby producing Cl ≦ 10 ppm, C ≦ 50 ppm, S < 50 ppm, O Mn of <30 ppm (refer to Patent Document 10).

This method is effective for high purity of manganese. An object of the present invention is to provide a production method and high-purity manganese which can further achieve high purity and can reduce cost.

Patent Document 1: Japanese Patent Laid-Open No. 53-8309

Patent Document 2: Japanese Laid-Open Patent Publication No. 2007-119854

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-285373

Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-167630

Patent Document 5: Japanese Patent Laid-Open No. Hei 11-100631

Patent Document 6: Japanese Patent Laid-Open No. Hei 11-152528

Patent Document 7: Japanese Patent Laid-Open No. 2011-068992

Patent Document 8: Japanese Laid-Open Patent Publication No. 2010-209384

Patent Document 9: Japanese Patent Laid-Open No. 2011-094207

Patent Document 10: Japanese Laid-Open Patent Publication No. 2013-142184

It is an object of the present invention to provide a high-purity manganese produced from commercially available electrolytic manganese and a method for producing the same, and in particular, the problem is that the amount of impurities is less than that of the prior art, and high-purity manganese is produced at low cost.

The present invention provides the following invention by solving the above problems.

1) A method for producing high-purity manganese, which comprises placing a manganese raw material in a magnesia crucible, using a vacuum induction melting furnace (VIM furnace) in an inactive environment of 500 Torr or less, and melting at a melting temperature of 1240 to 1400 ° C to a weight of manganese. Calcium (Ca) is added in the range of 0.5 to 2.0% for deoxidation and desulfurization. After deoxidation and desulfurization, it is cast into an iron mold to produce an ingot, and then the manganese ingot is filled in a shell. The melting furnace is heated by a vacuum pump to a pressure of 10 ^-5 Torr or less, and maintained in a molten state for 10 to 60 minutes, and then the melting reaction is terminated to obtain high-purity manganese.

2) A high-purity manganese, a high-purity manganese purified by vacuum induction melting (VIM) and shell melting, characterized by impurity elements B, Mg, Al, Si, S, Ca, The total amount of Cr, Fe, and Ni is 50 ppm or less, does not include a gas component element, and has a purity of 4N5 (99.995%) or more.

3) A high-purity manganese, a high-purity manganese purified by vacuum induction melting (VIM) and shell melting, characterized by impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, The total amount of Ni is 50 ppm or less, does not include a gas component element, and has a purity of 4N5 (99.995%) or more, and the gas components oxygen (O) and nitrogen (N) are each less than 10 ppm.

4) A high-purity manganese having a total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni of 50 ppm or less, excluding a gas component element, and having a purity of 4N5 (99.995%) or more.

5) A high-purity manganese, the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni is 50 ppm or less, excluding gas component elements, and has a purity of 4N5 (99.995%) or more, gas The components oxygen (O) and nitrogen (N) were each less than 10 ppm.

In addition, the unit "ppm" used in the present specification refers to "wtppm", excluding nitrogen (N) and oxygen (O) of gas component elements, and the analysis value of each element concentration is by GDMS (Glow Discharge Mass Spectrometry) The analysis was carried out by the method, and the analysis of the gas component elements (O, N) was carried out by using an oxygen and nitrogen analyzer manufactured by LECO Corporation. Moreover, the gas component element in the present invention means hydrogen (H), oxygen (O), nitrogen (N), and carbon (C). The same is true below.

According to the present invention, the following effects are obtained.

(1) High-purity manganese having a purity of 4N5 (99.995%) or more and a total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni of 50 ppm or less can be obtained, and a gas can be obtained. Each of the components O and N is less than 10 ppm of high-purity manganese.

(2) The following effects can be cited: according to the present invention, no special device is required, The production is carried out in a general-purpose furnace, and high-purity manganese or the like can be obtained at a low cost and in a high yield as compared with the conventional method, that is, the distillation method.

(3) Further, in the case of forming a sputtering target, there is an effect that a target having a small particle generation can be produced.

Figure 1 is a schematic illustration of a series of steps from raw material manganese, VIM melting, shell melting to high purity manganese.

Hereinafter, embodiments of the present invention will be described in detail.

In the method for producing high-purity manganese of the present invention, a commercially available (2N grade) sheet-shaped electrolytic manganese can be used as a raw material, and since the purity of the raw material is not affected, the type of the raw material is not particularly limited.

When manufacturing high-purity manganese, the manganese raw material is first placed in a magnesite crucible, and melted at a melting temperature of 1240 to 1400 ° C in an inert atmosphere of 500 Torr or less using a vacuum induction melting furnace (VIM furnace). If it is less than 1240 ° C, the manganese cannot be melted, so the VIM treatment cannot be performed.

If it exceeds 1400 ° C, it will be melted and mixed into the molten manganese due to the high temperature of the oxides and sulfides in the manganese melt, and the magnesium (Mg), calcium (Ca), and oxygen (MIM) after the VIM is melted. The concentration of sulfur (S) and the concentration of sulfur (S) may be in the range of several hundred ppm to several thousand ppm, and finally the purity of the object of the present invention cannot be achieved. This result is shown in Table 2.

Further, calcium is slowly added to the manganese melt in the range of 0.5 to 2.0% by weight of manganese to perform deoxidation and desulfurization. After the end of deoxidation and desulfurization, casting into an iron mold to produce an ingot. After the ingot is cooled, the slag adhering to the ingot is removed.

Next, the manganese ingot was placed in a shell type melting furnace, and the pressure was reduced to 10 ^-5 Torr or less by a vacuum pump to start heating, and the molten state was maintained for 10 to 60 minutes, and then the melting reaction was terminated to obtain high-purity manganese.

The manganese obtained by the production method can make the total amount of the impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni 50 ppm or less, excluding the gas component, and have 4 N 5 (99.995%) or more. Purity is high purity manganese.

Further, the total amount of the impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni may be 50 ppm or less, and the gas components O and N may each be less than 10 ppm.

In particular, O and N are present in an electronic device using manganese, and since an oxide or a nitride is formed, not only the characteristics of manganese itself are deteriorated, but also a composite material with Mn or an alloyed material may be generated. The influence of the formation of oxides or nitrides (deterioration of characteristics) or the influence of O or N diffusion between adjacent materials (deterioration of characteristics), therefore, the presence of Mn which reduces the O and N contents Extremely effective.

A summary of these steps is shown in Figure 1.

Shell melting can use a conventional shell melting device. In general, the shell furnace is cooled, and the raw material filled in the inside of the furnace is melted by induction heating, so that there is no characteristic of contamination from the furnace.

For the purification of Mn, the following concept is not existed in the prior art: by VIM melting, S and O are removed in advance by calcium (Ca), and then the shell furnace is used to remove the extremely increased Mg and Ca, and finally, The purity of Mn is high.

Example

In the following, the embodiments are described, but the embodiments are not limited by the examples or comparative examples in order to make the invention easy to understand.

(Example 1)

Commercially available flake-form electrolytic manganese (purity 2N: 99%) was used as a starting material. Raw material manganese impurity B: 15 ppm, Mg: 90 ppm, Al: 4.5 ppm, Si: 39 ppm, S: 280 ppm, Ca: 5.9 ppm, Cr: 2.9 ppm, Fe: 11 ppm, Ni: 10 ppm, O: 720 to 2500 ppm, N: 10~20ppm.

(VIM melting step)

The manganese raw material was placed in a magnesite crucible, and melted at a melting temperature of 1,300 ° C in an inert atmosphere of 200 Torr or less using a vacuum induction melting furnace (VIM furnace). Further, 1% by weight of manganese (Ca) by weight of manganese was slowly added to the manganese melt to carry out deoxidation and desulfurization. After the end of deoxidation and desulfurization, the manganese melt is cast into an iron mold to produce an ingot. After the ingot is cooled, the slag adhering to the ingot is removed.

The impurity of the ingot after the melting was B: 14 ppm, Mg: 160 ppm, Al: 1.2 ppm, Si: 16 ppm, S: 16 ppm, Ca: 520 ppm, Cr: 2.5 ppm, Fe: 3.6 ppm, Ni: 1.3 ppm, O : less than 10ppm, N: less than 10ppm. The results are shown in Table 1.

As shown in Table 1, it can be seen that since the calcium reduction step is performed, the calcium in the cast manganese is increased, and the Mg which is a constituent element of the magnesia crucible is easily reduced by calcium, and a part thereof is mixed in the manganese, and the Mg is greatly increased. However, S, O, and Ni are greatly reduced, and other elements are also reduced.

(shell melting step)

Next, the manganese ingot obtained by melting the above VIM is filled in a water-cooled crucible, and the crucible is placed in a shell melting furnace, and the vacuum pump is set to be 10 ⁻⁵ Torr or less, and heated by induction heating to confirm After the manganese ingot of the raw material is melted, it is maintained for 30 minutes, and then the melting is completed to obtain solidified manganese.

The impurity of this manganese ingot was B: 8.1 ppm, Mg: 1.9 ppm, Al: 1.7 ppm, Si: 16 ppm, S: 2.7 ppm, Ca: 9.4 ppm, Cr: 1.1 ppm, Fe: 3.6 ppm, Ni: 1.1 ppm , O: less than 10ppm, N: less than 10ppm.

The results are shown in Table 1 as such. As shown in Table 1, it was found that the calcium and magnesium which were increased by the first VIM melting were greatly reduced after the shell melting. Moreover, S is also reduced. This is believed to be due to shell melting to remove volatile impurities.

By adding the above-mentioned deoxidizing and desulfurizing agent to VIM melting and shell-type melting treatment, the manganese manganese raw material having a purity of 2N can be purified to 4N5 without including a gas component element.

Industrial availability

According to the present invention, manganese having extremely high purity can be obtained, and the manufacturing process is relatively simple, and the manufacturing cost can be reduced. Therefore, it is suitable as an electronic component material such as a wiring material, a magnetic material (magnetic head), and a metal manganese used for a semiconductor component material. A sputtering target for making a metal manganese film, especially a manganese-containing film. The present invention can be produced in a general-purpose furnace without requiring a special device, and has high industrial value because it can obtain high-purity manganese at a low cost and high productivity as compared with the conventional method, that is, the distillation method.

Claims (5)

A method for producing high-purity manganese, which comprises placing a manganese raw material in a magnesia crucible, using a vacuum induction melting furnace (VIM furnace) in an inactive environment of 500 Torr or less, and melting at a melting temperature of 1240 to 1400 ° C to a weight of 0.5 by weight of manganese. Calcium (Ca) is added in a range of ~2.0% for deoxidation and desulfurization. After deoxidation and desulfurization, it is cast into an iron mold to produce an ingot, and then the manganese ingot is filled in a shell melting furnace. (Skull melting furnace), heating is started by a vacuum pump to a pressure of 10 ^-5 Torr or less, and the molten state is maintained for 10 to 60 minutes, and then the melting reaction is terminated to obtain high-purity manganese. A high-purity manganese, purified by high-purity manganese by vacuum induction melting (VIM) and shell melting, characterized by impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni The total amount is 50 ppm or less, excluding gas component elements, and has a purity of 4N5 (99.995%) or more. A high-purity manganese, purified by high-purity manganese by vacuum induction melting (VIM) and shell melting, characterized by impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni The total amount is 50 ppm or less, excluding gas component elements, and has a purity of 4N5 (99.995%) or more, and the gas components oxygen (O) and nitrogen (N) are each less than 10 ppm. A high-purity manganese having a total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni of 50 ppm or less, excluding a gas component element, and having a purity of 4N5 (99.995%) or more. A high-purity manganese with a total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni below 50 ppm, excluding gas component elements, having a purity of 4N5 (99.995%) or more, gas component oxygen (O) and nitrogen (N) each did not reach 10 ppm.