WO2015060018A1 - Procédé pour produire du manganèse haute pureté et manganèse haute pureté - Google Patents

Procédé pour produire du manganèse haute pureté et manganèse haute pureté Download PDF

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Publication number
WO2015060018A1
WO2015060018A1 PCT/JP2014/072969 JP2014072969W WO2015060018A1 WO 2015060018 A1 WO2015060018 A1 WO 2015060018A1 JP 2014072969 W JP2014072969 W JP 2014072969W WO 2015060018 A1 WO2015060018 A1 WO 2015060018A1
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purity
ppm
sublimation
ingot
less
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PCT/JP2014/072969
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English (en)
Japanese (ja)
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和人 八木
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Jx日鉱日石金属株式会社
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Priority to JP2015510548A priority Critical patent/JP5925384B2/ja
Priority to KR1020157027721A priority patent/KR101664763B1/ko
Priority to US14/770,843 priority patent/US20160002749A1/en
Publication of WO2015060018A1 publication Critical patent/WO2015060018A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/003—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals by induction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

Definitions

  • the present invention relates to high-purity manganese (Mn) from commercially available electrolytic manganese (Mn) and a method for producing the same.
  • a commercially available method for producing metal Mn is an electrolytic method from an ammonium sulfate electrolytic bath.
  • sulfur (S) is about 100 to 3000 ppm
  • carbon (C) is also several hundred ppm.
  • Chlorine (Cl) is also several hundred ppm
  • oxygen (O) is contained in the order of several thousand ppm because it is an electrodeposit from the aqueous solution.
  • a sublimation purification method As a method for removing S and O from the electrolytic Mn, a sublimation purification method is well known in the prior art.
  • the sublimation purification method has a problem that the apparatus is very expensive and the yield is very bad.
  • S and O can be reduced by the sublimation purification method, it is contaminated due to the heater material, condenser material, etc. of the sublimation purification device, so metal Mn by the purification method is used as a raw material for electronic devices. There was a problem that it was not suitable.
  • Patent Document 1 a method for removing S in metal Mn is described in Patent Document 1 below, and Mn oxidation is performed at a melting temperature of Mn acid compounds such as MnO, Mn 3 O 4 , MnO 2 and / or metal Mn.
  • Mn acid compounds such as MnO, Mn 3 O 4 , MnO 2 and / or metal Mn.
  • Mn carbonate or the like is added, and the metal Mn to which the Mn compound is added is melted in an inert atmosphere, and is preferably kept in a molten state for 30 to 60 minutes, and the sulfur content: 0.002% It is described that.
  • this document 1 does not describe the contents of oxygen (O), nitrogen (N), carbon (C), and chlorine (Cl) at all, and has not yet solved the problems caused by the contents thereof. .
  • Patent Document 2 a method for electrolytically collecting metal Mn and high-purity metal Mn are dissolved in hydrochloric acid, and an undissolved material is filtered.
  • a method for electrolytic collection of metal Mn characterized by using an electrolyte prepared by filtering a product and adding a buffer, preferably adding metal Mn to a hydrochloric acid solution of metal Mn, Using electrolyte prepared by adding hydrogen peroxide and aqueous ammonia to the solution obtained by filtering undissolved material, filtering the precipitate formed under weakly acidic or neutral liquidity, and adding a buffer.
  • a method of performing electrowinning of metal Mn is described.
  • Patent Document 3 describes a method for producing high-purity Mn.
  • An ion-exchange purification method using a chelate resin is applied to an aqueous Mn chloride solution, and then the purified aqueous Mn chloride solution is purified by electrowinning. How to do is described.
  • the dry method describes that high-purity Mn is obtained from solid-phase Mn by vacuum sublimation purification method (Mn vapor obtained by sublimation of solid-phase Mn is selectively condensed and vapor-deposited in the cooling section by vapor pressure difference). Has been.
  • the document 3 describes that the total concentration of sulfur (S), oxygen (O), nitrogen (N), and carbon (C) is 10 ppm or less. However, this document 3 does not describe the content of chlorine (Cl) that is harmful to the manufacture of semiconductor components. Since Mn chloride is used as a raw material, there is a possibility that chlorine may be contained in a high concentration, which is problematic.
  • Patent Document 4 describes a method for producing a low-oxygen Mn material, and obtains a Mn material in which the oxygen content is reduced to 100 ppm or less by inductively skull-dissolving the Mn raw material in an inert gas atmosphere. There is a description that it is preferable to perform acid cleaning before induction skull dissolution of the Mn raw material because oxygen can be further reduced. However, in this document 4, there is a description regarding the reduction of oxygen (O), sulfur (S), and nitrogen (N) in high-purity Mn, but there is no description regarding the content of other impurities. The problem of inclusion has not been solved.
  • Patent Document 5 describes a Mn alloy material for magnetic material, a Mn alloy sputtering target, and a magnetic thin film, and has an oxygen (O) content of 500 ppm or less, a sulfur (S) content of 100 ppm or less, preferably further It is described that the content of impurities (elements other than Mn and alloy components) is 1000 ppm or less in total. Furthermore, the same literature describes a method for removing oxygen (O) and sulfur (S) by adding Ca, Mg, La, etc. as a deoxidizing / desulfurizing agent to commercially available electrolytic Mn, and performing high-frequency dissolution, It describes that it is purified by vacuum distillation after preliminary dissolution.
  • O oxygen
  • S sulfur
  • Example 3 In the above Mn raw material, in Example 3, a deoxidation / desulfurization agent was added and dissolved at high frequency, the oxygen content was 50 ppm, the sulfur content was 10 ppm (Table 3), and in Example 7, vacuum distillation was performed after preliminary dissolution. There is a description that the oxygen content is 30 ppm and the sulfur content is 10 ppm (Table 7). In these examples, Si is contained in an amount of about 10 to 20 ppm and Pb is contained in an amount of about 10 to 30 ppm.
  • Patent Document 6 describes a method for producing a high-purity Mn material and a high-purity Mn material for forming a thin film.
  • a high-purity Mn material is obtained by pre-dissolving crude Mn at 1250-1500 ° C. and then vacuum distillation at 1100-1500 ° C.
  • the degree of vacuum during vacuum distillation 5 ⁇ 10 - and 5 ⁇ 10 Torr.
  • the high-purity Mn thus obtained 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, carbon (C): 100 ppm or less.
  • Example 2 (Table 2) describes an example in which oxygen is 30 ppm and other elements are less than 10 ppm. However, also in this case, the impurity level does not reach the target level.
  • Patent Document 7 describes a sputtering target made of a high-purity Mn alloy
  • Patent Document 8 describes a method of recovering Mn using sulfuric acid
  • Patent Document 9 produces metal Mn by heat reduction of Mn oxide.
  • desulfurization there is no description regarding desulfurization.
  • the present inventors leached the Mn raw material with an acid, filtered the residue with a filter, and then used the filtered solution on the cathode side in electrolysis, and also removed the electrolytic Mn.
  • a high-purity Mn production method for producing Mn with ⁇ 50 ppm, S ⁇ 50 ppm, and O ⁇ 30 ppm was proposed (see Patent Document 10). This method is effective for increasing the purity of Mn.
  • the present invention is aimed at a manufacturing method and high-purity Mn that can achieve higher purity and can reduce costs.
  • An object of the present invention is to provide a high-purity Mn from a commercially available electrolytic Mn and a method for producing the same, and particularly, to produce a high-purity Mn at a low cost with a significantly smaller amount of impurities than the prior art. This is the issue.
  • a method for producing high-purity Mn in which a Mn raw material is put in a magnesia 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).
  • VIM furnace vacuum induction melting furnace
  • Calcium (Ca) is added in the range of 0.5 to 2.0% of the Mn weight to perform deoxidation and desulfurization, and after completion of the deoxidation and desulfurization, an ingot is produced by casting into an iron mold.
  • the Mn ingot is again put into the magnesia crucible, and the melting temperature is adjusted to 1200 to 1450 ° C.
  • the metal Mn ingot is put into an alumina crucible, and is heated to vacuum by a vacuum pump so that the pressure becomes 0.01 to 1 Torr.
  • a method for producing high purity Mn wherein a high purity Mn is obtained by performing a distillation reaction.
  • the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 50 ppm or less, and has a purity of 4N5 (99.995%) or more excluding gas components. Characteristic high purity Mn.
  • the gas component element in this invention means hydrogen (H), oxygen (O), nitrogen (N), and carbon (C). The following also means the same.
  • the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 10 ppm or less, and has a purity of 5N (99.999%) or more excluding gas components. Characteristic high purity Mn.
  • the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni is 50 ppm or less, and has a purity of 4N5 (99.995%) or more, excluding gas components, High-purity Mn, wherein O and N as gas components are each less than 10 ppm.
  • the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, Ni is 10 ppm or less, and has a purity of 5N (99.999%) or more, excluding gas components, High-purity Mn, wherein O and N as gas components are each less than 10 ppm.
  • ppm used in the present specification means “wtppm”, and the analysis values of each element concentration except for nitrogen (N) and oxygen (O) which are gas component elements are GDMS (Glow Discharge Mass). Spectrometry), and gas component elements were analyzed using an oxygen / nitrogen analyzer manufactured by LECO.
  • the present invention has the following effects. (1)
  • the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 50 ppm or less, excluding gas components, and having a purity of 4N5 (99.995%) or more
  • the total amount of purity Mn and impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 10 ppm or less, and excluding gas components, the purity is 5N (99.999%) or more.
  • High-purity Mn can be obtained.
  • O and N which are gas components can each be less than 10 ppm. (3) It can be produced in a general-purpose furnace without the need for special equipment, and has the effect of being able to obtain high-purity Mn at a low cost and in a high yield compared to the conventional distillation method. Can be done.
  • the method for producing high-purity Mn according to the present invention can use commercially available (2N level) flaky electrolytic Mn as a raw material, but since it does not affect the purity of the raw material, the type of the raw material is not particularly limited.
  • a Mn raw material is put in a magnesia 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) (primary VIM melting). . If it is less than 1240 ° C., VIM treatment cannot be performed because Mn does not melt.
  • VIM furnace vacuum induction melting furnace
  • the Mn ingot is again put in a magnesia crucible, and the melting temperature is adjusted to 1200 to 1450 ° C. and maintained for 10 to 60 minutes in an inert atmosphere of 200 Torr or less using a vacuum induction melting furnace (VIM furnace). (Secondary VIM dissolution). Thereafter, an ingot is manufactured by casting into an iron mold. After cooling the ingot, slag adhering to the ingot is removed.
  • VIM furnace vacuum induction melting furnace
  • the primary VIM melting step Ca, which is a deoxidizing / desulfurizing agent, is added to the molten Mn during melting, so a very small amount of Ca is contained in the Mn ingot after the primary melting, and the melting point of Mn is lowered.
  • the secondary VIM melting temperature can be dissolved even in a temperature range lower than the primary VIM melting temperature.
  • the deoxidation / desulfurization agent (Ca) mixed after the primary VIM dissolution can be removed. If the temperature of the secondary VIM dissolution exceeds 1450 ° C., the volatilization loss of Mn becomes very large, the yield decreases, and the cost increases, which is not preferable.
  • this metal Mn ingot is put into an alumina crucible, and is heated after being evacuated to 0.01 to 1 Torr with a vacuum pump, and then sublimation / distillation temperature is set to 1100 to 1250 ° C. Reaction is performed to produce high-purity Mn. Mn volatilized by the sublimation / distillation reaction is guided to the cooling cylinder, and the deposited Mn is recovered there. Preferably, the sublimation / distillation step is terminated when the amount of Mn recovered by the sublimation / distillation reaction reaches 70% of the weight of the Mn raw material filled in the alumina crucible. By this end operation, it is possible to prevent the impurity element remaining in the crucible from being sublimated and mixed into Mn adhered to the cooling cylinder, thereby lowering the purity. A summary of this process is shown in FIG.
  • Mn obtained by this manufacturing method is such that the total amount (total amount) of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 50 ppm or less, excluding gas components, and 4N5 (99 .995%) or higher purity Mn can be obtained.
  • the total amount (total amount) of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is set to 10 ppm or less, and 5N (99. High-purity Mn having a purity of 999%) or higher can be obtained.
  • it can be purified by setting the sublimation / distillation temperature to 1200 to 1250 ° C.
  • O and N which are gas components can each be less than 10 ppm.
  • a metal Mn ingot is placed in a cylindrical alumina crucible, and an alumina cylinder of the same shape is vertically stacked on the cylindrical crucible to perform the sublimation and distillation reaction.
  • High purity Mn can be produced by adhering Mn to the inside of the upper alumina cylinder. Since it is a structure in which cylindrical alumina crucibles (cylindrical bodies) are stacked, the structure is simple, and the structure of such an apparatus is a factor that can reduce manufacturing costs.
  • the cylindrical alumina crucible containing the metal Mn ingot needs to be heated, it can be heated by attaching a carbon heater to the outside of the crucible. Since this device structure is also simple, it is a factor that can reduce the manufacturing cost.
  • the sublimation / distillation purification it is desirable that Mn in the cylindrical alumina crucible is heated to 1100 to 1250 ° C. and the sublimation rate is 20 to 184 g / h. In this case, the sublimation / distillation purification time is approximately 8 to 75 hours.
  • the amount of impurities can be adjusted by adjusting the sublimation / distillation purification temperature and the sublimation rate, preferably the sublimation / distillation rate is 20 to 184 g / h, more preferably 103 to 184 g / h. It is.
  • the sublimation / distillation reaction step was completed when the amount of Mn to be coagulated and recovered reached 70% by weight (recovery rate) of the Mn raw material filled in the alumina crucible.
  • the impurity concentration in the raw material Mn increases, and the impurity element easily sublimates at the end of the process.
  • Example 1 Commercially available flaky electrolytic Mn (purity 2N: 99%) was used as a starting material.
  • the impurities of the raw material Mn are 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: 720-2500 ppm, N: 10-20 ppm.
  • Impurities of the ingot after this primary dissolution are B: 12 ppm, Mg: 130 ppm, Al: 1.2 ppm, Si: 20 ppm, S: 3.4 ppm, Ca: 520 ppm, Cr: 0.25 ppm, Fe: 2.2 ppm, Ni: 1.4 ppm, O: 10 ppm, N: 10 ppm.
  • Table 1 since it is a Ca reduction process, Ca is increased in the cast Mn, and Mg, which is a constituent element of the magnesia crucible, is easily reduced to Ca, and a part thereof is in the cast Mn. It can be seen that Mg increases, but S significantly decreases and other elements also decrease.
  • the Mn ingot obtained by the primary VIM melting is put again in the magnesia crucible, and the melting temperature is adjusted to 1400 ° C. in an inert atmosphere of 100 Torr or less using a vacuum induction melting furnace (VIM furnace) and 30 minutes. Maintained and performed secondary VIM dissolution. Thereafter, an ingot was manufactured by casting into an iron mold. After the ingot was cooled, the slag adhering to the ingot was removed.
  • VIM furnace vacuum induction melting furnace
  • Impurities of the ingot after this secondary dissolution are: B: 10 ppm, Mg: 13 ppm, Al: 1.9 ppm, Si: 20 ppm, S: 0.58 ppm, Ca: 25 ppm, Cr: 0.28 ppm, Fe: 2.4 ppm , Ni: 1.2 ppm, O: 10 ppm, N: 10 ppm.
  • Table 1 it can be seen that after secondary dissolution, Ca and Mg increased by primary dissolution are greatly reduced. Also, S is reduced. It is considered that impurities that are likely to volatilize were removed by secondary dissolution.
  • the metal Mn ingot obtained through the primary VIM melting step and the secondary VIM melting step is placed in a cylindrical alumina crucible, and the cylindrical body of the same shape is vertically stacked on the cylindrical crucible. Sublimation and distillation reactions were performed. After evacuating to 0.1 Torr with a vacuum pump, heating was performed, and Mn sublimation and distillation reaction were performed. And Mn was adhered inside the upper alumina cylindrical body, and high purity Mn was obtained. The cylindrical alumina crucible containing the Mn ingot was heated with a carbon heater attached to the outside of the crucible.
  • the sublimation / distillation purification Mn in the cylindrical alumina crucible was heated to 1050 to 1250 ° C., and the sublimation rate was 3 to 184 g / h. In this case, the sublimation purification time was about 8 to 75 hours.
  • the effect of removing impurities by sublimation / distillation purification is greatly influenced by the heating temperature and the sublimation / distillation rate. Therefore, as described above, the sublimation / distillation rate is 3 to 184 g / h in the range of 1050 to 1250 ° C. Implement step by step in scope. Specific examples (Examples and Comparative Examples) are shown below.
  • the sublimation / distillation process is completed, and impurities in the distilled Mn are removed. Mixing was prevented.
  • the relationship between the heating temperature and the sublimation / distillation rate is examined in advance, the amount of Mn adhered from the sublimation / distillation rate for each heating temperature is calculated, and the process end time is determined. To do.
  • Example 1-1 Sublimation and distillation purification were performed at a heating temperature of 1100 ° C. and a sublimation rate of 23 (g / h).
  • the impurities of the metal Mn after the sublimation purification are B: 0.61 ppm, Mg: 17 ppm, Al: 0.25 ppm, Si: 0.28 ppm, S: 0.07 ppm, Ca: 7.3 ppm, Cr: 0.05 ppm Fe ⁇ 0.1 ppm, Ni: 0.03 ppm, O ⁇ 10 ppm, N ⁇ 10 ppm.
  • Table 1 the effect of sublimation purification was sufficient, and the target purity of 4N5 (99.995%) or higher could be achieved. This is the preferred embodiment.
  • Example 1-2 Sublimation / distillation purification was performed at a heating temperature of 1200 ° C. and a sublimation rate of 103 (g / h).
  • the impurities of the metal Mn after the sublimation purification are B: 0.46 ppm, Mg: 0.17 ppm, Al: 1.4 ppm, Si: 1.2 ppm, S: 0.02 ppm, Ca: 2.1 ppm, Cr: 0 .69 ppm, Fe: 0.21 ppm, Ni: 0.08 ppm, O ⁇ 10 ppm, N ⁇ 10 ppm.
  • Table 1 the effect of sublimation purification was sufficient, and the target purity of 5N (99.999%) or more could be achieved. This is a more preferred embodiment.
  • Example 1-3 Sublimation / distillation purification was performed at a heating temperature of 1250 ° C. and a sublimation rate of 184 (g / h).
  • the impurities of the metal Mn after the sublimation purification are B: 1.1 ppm, Mg ⁇ 0.01 ppm, Al: 0.85 ppm, Si: 3.6 ppm, S: 0.04 ppm, Ca: 1.9 ppm, Cr: 1 .4 ppm, Fe: 0.77 ppm, Ni: 0.18 ppm, O ⁇ 10 ppm, N ⁇ 10 ppm.
  • Table 1 the effect of sublimation purification was sufficient, and the target purity of 5N (99.999%) or more could be achieved. This is the preferred embodiment.
  • Mn with extremely high purity can be obtained, the manufacturing process is relatively simple, and the manufacturing cost can be reduced. Therefore, electronic component materials such as wiring materials and magnetic materials (magnetic heads), semiconductor components, etc. It is useful as a sputtering target material for producing a metal Mn used for the material, the same thin film, particularly a Mn-containing thin film. Since the present invention can be produced in a general-purpose furnace without requiring a special apparatus and can obtain high-purity Mn at a low cost and in a high yield as compared with the conventional distillation method, It can be said that the utility value of is high.

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Abstract

La présente invention concerne un procédé pour produire du Mn haute pureté consistant à : placer un matériau de départ de Mn électrolytique en écailles dans un creuset en magnésie et le faire fondre à une température de fusion de 1240-1400°C à l'aide d'un four de fusion à induction sous vide (four FIV) sous une atmosphère inerte de 500 torrs ou moins ; ajouter du calcium dans une plage de 0,5-2,0% du poids de Mn pour réaliser une désoxygénation et une désulfurisation ; après la fin de la désoxygénation et la désulfurisation, produire un lingot par déversement dans un moule en fer ; puis placer ledit lingot de Mn à nouveau dans le creuset en magnésie, ajuster la température de fusion à 1200-1450°C à l'aide du four de fusion à induction sous vide (four FIV) sous une atmosphère inerte de 200 torrs ou moins et la maintenir pendant 10-60 minutes ; puis déverser dans un moule en fer pour produire un lingot ; ensuite, placer ledit lingot de Mn métallique dans un creuset en oxyde d'aluminium ; et chauffer après mise sous vide à 0,1 torr à l'aide d'une pompe à vide pour réaliser des réactions de sublimation et de distillation. La présente invention concerne un procédé pour produire du Mn métallique haute pureté à partir de Mn électrolytique commercialement disponible. En particulier, la présente invention concerne le problème d'obtention de Mn métallique haute pureté présentant de faibles quantités d'impuretés telles que B, Mg, Al et Si.
PCT/JP2014/072969 2013-10-25 2014-09-02 Procédé pour produire du manganèse haute pureté et manganèse haute pureté WO2015060018A1 (fr)

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JP2015510548A JP5925384B2 (ja) 2013-10-25 2014-09-02 高純度マンガンの製造方法及び高純度マンガン
KR1020157027721A KR101664763B1 (ko) 2013-10-25 2014-09-02 고순도 망간의 제조 방법
US14/770,843 US20160002749A1 (en) 2013-10-25 2014-09-02 Method for manufacturing high purity manganese and high purity manganese

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JP2021088744A (ja) * 2019-12-04 2021-06-10 株式会社 大阪アサヒメタル工場 高純度マンガンの製造方法および高純度マンガン
CN113897501A (zh) * 2021-09-30 2022-01-07 宁波创致超纯新材料有限公司 一种真空蒸馏提纯金属锰的方法

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