WO2015060018A1 - Method for manufacturing high purity manganese and high purity manganese - Google Patents
Method for manufacturing high purity manganese and high purity manganese Download PDFInfo
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- 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
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- 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
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Abstract
Description
しかしながら、この文献3には、半導体部品の製造に有害である塩素(Cl)の含有量の記載がない。原料として塩化Mnを使用していることから、塩素が高濃度に含有される可能性があり、問題を有している。 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.
さらに、同文献には、市販されている電解Mnに脱酸・脱硫剤としてCa,Mg,La等を加え、高周波溶解を行うことによって酸素(O)、硫黄(S)を除去する方法や、予備溶解後に真空蒸留して高純度化することが記載されている。 Patent Document 5 below 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.
この方法は、Mnの高純度化に有効である。本願発明は、さらに高純度化を達成でき、かつコスト低減が可能である製造方法と高純度Mnを目途とするものである。 From the above, 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 method for producing high-purity Mn having a Cl content of 100 ppm or less in the electrolytic Mn by gas treatment, and further by degassing the electrolytic Mn raw material and dissolving it in an inert atmosphere, Cl ≦ 10 ppm, C 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.
1)高純度Mnの製造方法であって、Mn原料をマグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて500Torr以下の不活性雰囲気下、溶解温度1240~1400°Cで溶解後、カルシウム(Ca)をMn重量の0.5~2.0%の範囲で添加して脱酸及び脱硫を行い、脱酸及び脱硫の終了後鉄製鋳型に鋳込でインゴットを製造し、次にこのMnインゴットを再度マグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて200Torr以下の不活性雰囲気下、溶解温度を1200~1450°Cに調整すると共に10~60分間維持し、その後鉄製鋳型に鋳込みインゴットを製造し、次にこの金属Mnインゴットをアルミナ坩堝に入れ、真空ポンプで0.01~1Torrになるように真空に引いた後加熱を行い、昇華及び蒸留反応を行って高純度Mnを得ることを特徴とする高純度Mnの製造方法。 The present invention solves the above problems and provides the following inventions.
1) 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). 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. and maintained for 10 to 60 minutes under an inert atmosphere of 200 Torr or less using a vacuum induction melting furnace (VIM furnace), and then the iron mold Then, 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. And a method for producing high purity Mn, wherein a high purity Mn is obtained by performing a distillation reaction.
5)昇華及び蒸留精製工程において、昇華・蒸留されたMnの凝着量がアルミナ坩堝内に充填した金属Mnインゴット重量の70%に達した時点で昇華・蒸留工程を終了することを特徴とする前記1)~4)のいずれか一項に記載の高純度Mnの製造方法。 4) The method for producing high-purity Mn according to any one of 1) to 3) above, wherein the purification by sublimation distillation is performed at 1100 to 1250 ° C. and the sublimation rate is 20 to 184 g / h.
5) In the sublimation and distillation purification process, the sublimation / distillation process is terminated when the amount of adhesion of sublimated / distilled Mn reaches 70% of the weight of the metal Mn ingot filled in the alumina crucible. The method for producing high-purity Mn according to any one of 1) to 4).
7)不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が10ppm以下であり、ガス成分を除き、5N(99.999%)以上の純度を有することを特徴とする高純度Mn。 6) 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. In addition, the gas component element in this invention means hydrogen (H), oxygen (O), nitrogen (N), and carbon (C). The following also means the same.
7) 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.
(1)不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が50ppm以下であり、ガス成分を除き、4N5(99.995%)以上の純度を有する高純度Mn、さらには不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が10ppm以下であり、ガス成分を除き、5N(99.999%)以上の純度を有する高純度Mnを得ることができる。 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.
(3)特別な装置を必要とせずに、汎用炉で製造可能であり、従来法である蒸留法と比較して低コストかつ高収率で高純度Mnを得ることができる等の効果を挙げられることができる。 (2) Furthermore, 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.
本願発明の高純度Mnの製造方法は、市販(2Nレベル)のフレーク状電解Mnを原料として使用できるが、原料の純度には影響しないので、原料の種類には、特に制限はない。 Hereinafter, embodiments of the present invention will be described in detail.
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.
1240℃未満ではMnが融解しないためVIM処理することができない。1400℃を超えると、酸化物、硫化物の浮遊物が高温のため再融解してMn中に取り込まれ、一次VIM溶解後のマグネシウム(Mg)、カルシウム(Ca)、酸素(O)及び硫黄(S)の濃度が数百ppm~千ppmオーダーとなり、最終的に本発明の目的の純度を達成することができない。この結果を、表2に示す。 When producing high-purity Mn, first, 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. When the temperature exceeds 1400 ° C., oxide and sulfide suspended matter is remelted due to high temperature and taken into Mn, and after dissolution of primary VIM, magnesium (Mg), calcium (Ca), oxygen (O) and sulfur ( The concentration of S) is on the order of several hundred ppm to 1,000 ppm, and finally the target purity of the present invention cannot be achieved. The results are shown in Table 2.
また、二次VIM溶解では、一次VIM溶解後に混入した脱酸・脱硫剤(Ca)を除去することができる。2次VIM溶解の温度が1450℃を超えると、Mnの揮発ロスが非常に多くなり、収率が低下して、コストが上昇するので、好ましくない。 Here, in 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.
Further, in the secondary VIM dissolution, 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.
尚、好ましくは、昇華・蒸留反応で回収されるMnの量はアルミナ坩堝に充填されたMn原料の重量の70%に達した段階で昇華・蒸留工程を終了する。この終了操作によって、坩堝内に残留する不純物元素が昇華して、冷却筒に凝着されたMn中に混入して、純度が低下することを防止できる。この工程の概要の一覧を、図1に示す。 Next, 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.
そして、昇華精製に際して、ガス成分であるO、Nを、それぞれ10ppm未満とすることができる。 Furthermore, by changing the conditions for the sublimation / distillation purification, 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. Specifically, it can be purified by setting the sublimation / distillation temperature to 1200 to 1250 ° C.
And in the sublimation purification, O and N which are gas components can each be less than 10 ppm.
円筒状のアルミナ坩堝(円筒体)を重ねた構造なので、単純形であり、このような装置の構造は、製造コストを低減できる要因となる。 When performing the sublimation and distillation reaction, 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.
昇華・蒸留精製に際しては、円筒状アルミナ坩堝内のMnを1100~1250°Cに加熱し、昇華速度を20~184g/hで行うことが望ましい。この場合、昇華・蒸留精製の時間は、およそ8~75時間である。
昇華・蒸留精製の温度と昇華速度を調整することにより、不純物の量を調節することができ、好ましくは、昇華・蒸留速度を20~184g/hであり、より好ましくは、103~184g/hである。 Although 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.
In 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.
昇華・蒸留工程では蒸留が進行していくと、原料Mn中の不純物濃度が高くなり、工程の終盤時期には不純物元素が昇華しやすくなるためであり、凝着回収されるMnが原料Mnの70重量%に達した時点で終了することで、蒸留Mn中への不純物の混入が防止できる。 Further, 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.
As distillation proceeds in the sublimation / distillation process, the impurity concentration in the raw material Mn increases, and the impurity element easily sublimates at the end of the process. By completing the process when it reaches 70% by weight, it is possible to prevent the impurities from being mixed into distilled Mn.
出発原料として、市販のフレーク状電解Mn(純度2N:99%)を使用した。原料Mnの不純物は、B:15ppm、Mg:90ppm、Al:4.5ppm、Si:39ppm、S:280ppm、Ca:5.9ppm、Cr:2.9ppm、Fe:11ppm、Ni:10ppm、O:720~2500ppm、N:10~20ppmであった。 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.
上記Mn原料をマグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて200Torr以下の不活性雰囲気下で、溶解温度を1300°Cとし、溶解した。そして、このMn溶湯に、CaをMn重量の1重量%を、徐々に添加して脱酸及び脱硫を行った。脱酸及び脱硫の終了後、鉄製鋳型に鋳込でインゴットを製造した。インゴットの冷却後、インゴットに付着していたスラグは除去した。 (Primary VIM dissolution process)
The Mn raw material was put in a magnesia crucible and melted at a melting temperature of 1300 ° C. in an inert atmosphere of 200 Torr or less using a vacuum induction melting furnace (VIM furnace). Then, deoxidation and desulfurization were performed by gradually adding 1% by weight of Ca to the Mn melt. After completion of deoxidation and desulfurization, an ingot was produced by casting into an iron mold. After the ingot was cooled, the slag adhering to the ingot was removed.
この表1に示す通り、Ca還元の工程なので、鋳造されたMn中にCaが増加しており、またマグネシア坩堝の構成元素であるMgは、Caに還元されやすく、その一部が鋳造Mn中に混入して、Mgは増加しているが、Sが大きく低減し、他の元素も低減しているのが分かる。 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. The results are shown in Table 1.
As shown in 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.
次に、一次VIM溶解で得たMnインゴットを、再度マグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて100Torr以下の不活性雰囲気下、溶解温度を1400°Cに調整すると共に30分間維持して、二次VIM溶解を行った。その後、鉄製鋳型に鋳込みインゴットを製造した。インゴットの冷却後、インゴットに付着していたスラグは除去した。 (Secondary VIM dissolution process)
Next, 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.
表1に示す通り、二次溶解後には、一次溶解で増加したCaとMgが大きく低減しているのが分かる。また、Sも低減している。これは二次溶解により、揮発し易い不純物が除去されたと考えられる。 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. The results are also shown in Table 1.
As shown in 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.
上記の一次VIM溶解工程及び二次VIM溶解工程を経て得られた金属Mnインゴットを円筒状のアルミナ坩堝に入れ、この円筒状の坩堝の上に、同形状のアルミナの円筒体を垂直に重ね合わせ、昇華及び蒸留反応を行った。
真空ポンプで0.1Torrに真空に引いた後、加熱を行い、Mnの昇華及び蒸留反応を実施した。そして、上部のアルミナ円筒体の内部にMnを凝着させ、高純度Mnを得た。なお、Mnインゴットを入れた円筒状アルミナ坩堝は、坩堝の外側にカーボンヒータを装着して加熱した。 (Sublimation / distillation reaction process)
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.
昇華・蒸留精製による不純物の除去効果は、加熱温度と昇華・蒸留速度に大きく影響を受けるので、上記の通り、1050~1250°Cの範囲で、かつ昇華・蒸留速度を3~184g/hの範囲で、段階的に実施する。下記に具体例(実施例と比較例)を示す。 In 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.
(比較例1)
加熱温度:1050°C、昇華速度:3(g/h)として、昇華・蒸留精製を実施した場合
この昇華精製後の金属Mnの不純物は、B:0.2ppm、Mg:20ppm、Al:0.15ppm、Si:0.05ppm、S:0.03ppm、Ca:30ppm、Cr:0.05ppm、Fe<0.1ppm、Ni:0.01ppm、O<10ppm、N<10ppmとなった。この結果を、表1に示す。 (Impurities related to heating temperature and sublimation speed of sublimation purification)
(Comparative Example 1)
When sublimation / distillation purification is performed at a heating temperature of 1050 ° C. and a sublimation rate of 3 (g / h), the impurities of metal Mn after the sublimation purification are B: 0.2 ppm, Mg: 20 ppm, Al: 0 .15 ppm, Si: 0.05 ppm, S: 0.03 ppm, Ca: 30 ppm, Cr: 0.05 ppm, Fe <0.1 ppm, Ni: 0.01 ppm, O <10 ppm, N <10 ppm. The results are shown in Table 1.
加熱温度:1100°C、昇華速度:23(g/h)として、昇華・蒸留精製を実施した。
この昇華精製後の金属Mnの不純物は、B:0.61ppm、Mg:17ppm、Al:0.25ppm、Si:0.28ppm、S:0.07ppm、Ca:7.3ppm、Cr:0.05ppm、Fe<0.1ppm、Ni:0.03ppm、O<10ppm、N<10ppmとなった。この結果を、同様に、表1に示す。
この場合、昇華精製の効果が十分であり、本願の目的とする4N5(99.995%)以上の純度を、達成することができた。これは好適な実施例である。 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. The results are similarly shown in Table 1.
In this case, 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.
加熱温度:1200°C、昇華速度:103(g/h)として、昇華・蒸留精製を実施した。
この昇華精製後の金属Mnの不純物は、B:0.46ppm、Mg:0.17ppm、Al:1.4ppm、Si:1.2ppm、S:0.02ppm、Ca:2.1ppm、Cr:0.69ppm、Fe:0.21ppm、Ni:0.08ppm、O<10ppm、N<10ppmとなった。この結果を、同様に、表1に示す。
この場合、昇華精製の効果が十分であり、本願の目的とする5N(99.999%)以上の純度を達成することができた。これはさらに好適な実施例である。 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. The results are similarly shown in Table 1.
In this case, 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.
加熱温度:1250°C、昇華速度:184(g/h)として、昇華・蒸留精製を実施した。
この昇華精製後の金属Mnの不純物は、B:1.1ppm、Mg<0.01ppm、Al:0.85ppm、Si:3.6ppm、S:0.04ppm、Ca:1.9ppm、Cr:1.4ppm、Fe:0.77ppm、Ni:0.18ppm、O<10ppm、N<10ppmとなった。この結果を、同様に、表1に示す。
この場合、昇華精製の効果が十分であり、本願の目的とする5N(99.999%)以上の純度を達成することができた。これは好適な実施例である。 (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. The results are similarly shown in Table 1.
In this case, 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.
Claims (9)
- 高純度Mnの製造方法であって、Mn原料をマグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて500Torr以下の不活性雰囲気下、溶解温度1240~1400°Cで溶解し、CaをMn重量の0.5~2.0%の範囲で添加して脱酸及び脱硫を行い、脱酸及び脱硫の終了後鉄製鋳型に鋳込でインゴットを製造し、次にこのMnインゴットを再度マグネシア坩堝に入れ、真空誘導溶解炉(VIM炉)を用いて200Torr以下の不活性雰囲気下、溶解温度を1200~1450°Cに調整すると共に10~60分間維持し、その後鉄製鋳型に鋳込みインゴットを製造し、次にこの金属Mnインゴットをアルミナ坩堝に入れ、真空ポンプで0.01~1Torrになるように真空に引いた後加熱を行い、昇華及び蒸留反応を行って高純度Mnを得ることを特徴とする高純度Mnの製造方法。 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). Deoxidation and desulfurization are carried out by adding in the range of 0.5 to 2.0% of the Mn weight, and after completion of the deoxidation and desulfurization, an ingot is produced by casting into an iron mold, and then this Mn ingot is again magnesia. Place in a crucible and adjust the melting temperature to 1200-1450 ° C in an inert atmosphere of 200 Torr or less using a vacuum induction melting furnace (VIM furnace) and maintain for 10-60 minutes, then cast into an iron mold to produce an ingot Next, this metal Mn ingot is placed in an alumina crucible, and after being evacuated to 0.01 to 1 Torr with a vacuum pump, heating is performed to perform sublimation and distillation reactions. A method for producing high-purity Mn, characterized in that high-purity Mn is obtained.
- 前記昇華及び蒸留反応を行う際に、金属Mnインゴットを円筒状のアルミナ坩堝に入れ、この円筒状の坩堝の上に、同形状のアルミナの円筒体を垂直に重ね合わせて、昇華及び蒸留反応を行い、上部のアルミナ円筒体の内部にMnを凝着させることを特徴とする請求項1に記載の高純度Mnの製造方法。 When performing the sublimation and distillation reaction, 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. The method for producing high-purity Mn according to claim 1, wherein Mn is adhered to the inside of the upper alumina cylindrical body.
- 前記金属Mnインゴットを入れた円筒状アルミナ坩堝の外側にカーボンヒータを装着して加熱することを特徴とする請求項1又は2に記載の高純度Mnの製造方法。 The method for producing high-purity Mn according to claim 1 or 2, wherein a carbon heater is attached to the outside of the cylindrical alumina crucible containing the metal Mn ingot and heated.
- 昇華及び蒸留精製を1100~1250°Cで行い、昇華及び蒸留速度を20~184g/hで行うことを特徴とする請求項1~3のいずれか一項に記載の高純度Mnの製造方法。 The method for producing high-purity Mn according to any one of claims 1 to 3, wherein sublimation and distillation purification are performed at 1100 to 1250 ° C, and a sublimation and distillation rate is 20 to 184 g / h.
- 昇華及び蒸留精製工程において、昇華・蒸留されたMnの凝着量がアルミナ坩堝内に充填した金属Mnインゴット重量の70%に達した時点で昇華・蒸留工程を終了することを特徴とする請求項1~4のいずれか一項に記載の高純度Mnの製造方法。 The sublimation / distillation process is terminated when the amount of adhesion of sublimated / distilled Mn in the sublimation and distillation purification process reaches 70% of the weight of the metal Mn ingot filled in the alumina crucible. The method for producing high-purity Mn according to any one of 1 to 4.
- 不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が50ppm以下であり、ガス成分を除き4N5(99.995%)以上の純度を有することを特徴とする高純度Mn。 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. High purity Mn.
- 不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が10ppm以下であり、ガス成分を除き5N(99.999%)以上の純度を有することを特徴とする高純度Mn。 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 5 N (99.999%) or more excluding gas components. High purity Mn.
- 不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が50ppm以下であり、ガス成分を除き4N5(99.995%)以上の純度を有し、ガス成分であるO、Nがそれぞれ10ppm未満であることを特徴とする高純度Mn。 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. High purity Mn characterized in that certain O and N are each less than 10 ppm.
- 不純物元素であるB、Mg、Al、Si、S、Ca、Cr、Fe、Niの総量が10ppm以下であり、ガス成分を除き5N(99.999%)以上の純度を有し、ガス成分であるO、Nがそれぞれ10ppm未満であることを特徴とする高純度Mn。 The total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe, and Ni is 10 ppm or less, has a purity of 5 N (99.999%) or more, excluding gas components, High purity Mn characterized in that certain O and N are each less than 10 ppm.
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JP2021088744A (en) * | 2019-12-04 | 2021-06-10 | 株式会社 大阪アサヒメタル工場 | Method for manufacturing high purity manganese and high purity manganese |
CN113897501A (en) * | 2021-09-30 | 2022-01-07 | 宁波创致超纯新材料有限公司 | Method for purifying manganese metal by vacuum distillation |
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