JP5463644B2 - Method for refining molten metal - Google Patents
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- JP5463644B2 JP5463644B2 JP2008255996A JP2008255996A JP5463644B2 JP 5463644 B2 JP5463644 B2 JP 5463644B2 JP 2008255996 A JP2008255996 A JP 2008255996A JP 2008255996 A JP2008255996 A JP 2008255996A JP 5463644 B2 JP5463644 B2 JP 5463644B2
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- 238000007670 refining Methods 0.000 title claims description 38
- 229910052751 metal Inorganic materials 0.000 title claims description 27
- 239000002184 metal Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 27
- 239000002893 slag Substances 0.000 claims description 85
- 239000003607 modifier Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 158
- 239000000395 magnesium oxide Substances 0.000 description 79
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- 238000007664 blowing Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- 235000012255 calcium oxide Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000010459 dolomite Substances 0.000 description 5
- 229910000514 dolomite Inorganic materials 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 MgCO 3 content Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
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Description
本発明は、ＭｇＯを主体とする内張り耐火物を備えた精錬容器で行う溶融金属の精錬方法に関する。 The present invention relates to a molten metal refining method performed in a refining vessel provided with a refractory lining mainly composed of MgO.
転炉などの精錬容器を用いて行われる鉄鋼精錬では、スラグの塩基度（ＣａＯ／ＳｉＯ２）を高くすると脱Ｐ反応が促進されるため、炉体の長寿命化のために炉体内張り耐火物にはＭｇＯを主体とした塩基性耐火物（例えば、マグネシア・カーボンレンガなど）が使用されている。しかし、この内張り耐火物は、流動する溶融スラグとの接触によって溶損（耐火物の脱炭とそれに伴うマグネシア粒の脱落による溶損）しやすい問題がある。
従来、内張り耐火物の溶損を抑える方法として、吹錬中にＣａＯ原料やＭｇＯ原料を投入し、スラグ中のＣａＯ濃度、ＭｇＯ濃度を高める方法が知られている。この方法では、ＣａＯ原料として生石灰、石灰石などが、ＭｇＯ原料として生ドロマイト、軽焼ドロマイト、マグネシアクリンカーなどが用いられる。
In steel refining using a refining vessel such as a converter, the de-P reaction is promoted by increasing the basicity of slag (CaO / SiO 2 ). Basic refractories mainly composed of MgO (for example, magnesia, carbon brick, etc.) are used. However, this lining refractory has a problem that it is easily melted by contact with the flowing molten slag (melting due to decarburization of the refractory and accompanying dropping of magnesia grains).
Conventionally, as a method for suppressing melting loss of the lining refractory, a method is known in which a CaO raw material or an MgO raw material is introduced during blowing to increase the CaO concentration or MgO concentration in the slag. In this method, quick lime, limestone, or the like is used as the CaO raw material, and raw dolomite, light-burned dolomite, magnesia clinker, or the like is used as the MgO raw material.
例えば、特許文献１には、ＣａＯ原料、ＭｇＯ原料およびＦｅ２Ｏ３原料を混合・焼成して得られたものであって、構成成分として、カルシウムフェライト、ＣａＯおよびＭｇＯを含むスラグ成分調整剤を、上記のような方法に使用することが提案されている。この方法によれば、スラグ成分調整剤中のカルシウムフェライトが、従来使用されている生石灰や石灰石などのＣａＯ原料に較べて溶融温度が低いため、スラグに迅速に溶解して早期にスラグ塩基度を高めることができ、且つＭｇＯも早期にスラグ中に溶解してスラグ中のＭｇＯ濃度を高めることができるため、内張り耐火物の溶損を効果的に抑制できるとしている。
しかし、特許文献１の方法では、スラグ成分調整剤が焼成物であり、揮発分が残っていないため、スラグの溶解は固化体表面からとなる。このため、吹錬中に投入されたスラグ成分調整剤の溶解が不十分であり、内張り耐火物の溶損を抑制することはできるものの、その効果は十分ではない。
一方、溶解性の高いスラグ成分調整剤として、粉体ＭｇＯ（軽焼ＭｇＯ）に水を加えて成形したスラグ成分調整剤の使用が考えられる。このスラグ成分調整剤は、ＭｇＯの一部が水和してＭｇ（ＯＨ）２となり、ＭｇＯとＭｇ（ＯＨ）２とが混合した成形体として使用されることになると考えられる。しかし、本発明者らが検討した結果では、このようなスラグ成分調整剤を炉に投入すると、炉口から噴出するフレームが大きくなり、操業に支障をきたす場合があることが判明した。そして、その原因について調査・検討した結果、Ｍｇ（ＯＨ）２からのＨ２Ｏの乖離温度が２５０〜３００℃と低いため、スラグ成分調整剤の投入と同時にＨ２Ｏが発生し、炉口からのガス吹き出しが大きくなるためであることが判った。
However, in the method of
On the other hand, as a highly soluble slag component adjusting agent, use of a slag component adjusting agent formed by adding water to powdered MgO (light calcined MgO) can be considered. This slag component modifier is considered to be used as a molded body in which a part of MgO is hydrated to become Mg (OH) 2 and MgO and Mg (OH) 2 are mixed. However, as a result of investigations by the present inventors, it has been found that when such a slag component adjusting agent is introduced into the furnace, the frame ejected from the furnace port becomes large, which may hinder the operation. And as a result of investigating and examining the cause, since the detachment temperature of H 2 O from Mg (OH) 2 is as low as 250 to 300 ° C., H 2 O is generated simultaneously with the introduction of the slag component modifier, It turned out that it was because the gas blowing out from became large.
したがって本発明の目的は、上記のような従来技術の課題を解決し、炉に投入したスラグ成分調整剤を速やかに溶解させ、内張り耐火物の溶損を効果的に抑制することができるとともに、スラグ成分調整剤を投入した際に炉口からの急激なガス吹き出しを防止することができる溶融金属の精錬方法を提供することにある。 Therefore, the object of the present invention is to solve the above-described problems of the prior art, quickly dissolve the slag component modifier charged in the furnace, and effectively suppress the erosion loss of the lining refractory, An object of the present invention is to provide a molten metal refining method capable of preventing a sudden gas blow-out from a furnace port when a slag component modifier is introduced.
上記課題を解決するための本発明の要旨は以下のとおりである。
［1］ＭｇＯを主体とする内張り耐火物を備えた精錬容器にて溶融金属の精錬を行う方法において、Ｍｇ含有原料を主材とする粉粒状原料を成形し、固化させた成形体であって、ＭｇＯ、ＭｇＣＯ ３ およびＭｇ（ＯＨ） ２ を主成分とするスラグ成分調整剤を、精錬容器に投入して溶融金属の精錬を行うことを特徴とする溶融金属の精錬方法。
The gist of the present invention for solving the above problems is as follows.
[1] In a method for refining molten metal in a refining vessel equipped with a refractory lining mainly composed of MgO, a molded body obtained by molding and solidifying a powdery raw material mainly composed of a Mg-containing raw material. A molten metal refining method, comprising adding a slag component adjusting agent mainly composed of MgO, MgCO 3 and Mg (OH) 2 to a refining vessel to refining the molten metal.
［2］上記［1］の溶融金属の精錬方法において、スラグ成分調整剤は、バインダーとして水または／および有機物質を加えて混練した粉粒状原料を成形し、固化させた成形体であることを特徴とする溶融金属の精錬方法。 [2] In the molten metal refining method of [1 ] above, the slag component modifier is a molded body obtained by molding and solidifying a powdery raw material kneaded by adding water or / and an organic substance as a binder. A method for refining molten metal .
［3］上記［1］または［2］の溶融金属の精錬方法において、スラグ成分調整剤は、含有するＭｇ化合物中での割合で、ＭｇＯ含有量が３５〜８０質量％、ＭｇＣＯ３含有量が１５〜５０質量％、Ｍｇ（ＯＨ）２含有量が５〜４０質量％であることを特徴とする溶融金属の精錬方法。
［4］上記［1］〜［3］のいずれかの溶融金属の精錬方法において、スラグ成分調整剤は、さらにＣａＣＯ３を含有することを特徴とする溶融金属の精錬方法。
［5］上記［1］〜［4］のいずれかの溶融金属の精錬方法において、スラグ成分調整剤は、Ig.Loss量が１５〜３５質量％であることを特徴とする溶融金属の精錬方法。
[3] In the method for refining a molten metal according to [1] or [2] , the slag component modifier is a ratio in the Mg compound contained, and the MgO content is 35 to 80% by mass, and the MgCO 3 content is 15-50 mass%, Mg (OH) 2 content is 5-40 mass%, The refining method of the molten metal characterized by the above-mentioned.
[4] The molten metal refining method according to any one of the above [1] to [3] , wherein the slag component adjusting agent further contains CaCO 3 .
[5] The molten metal refining method according to any one of [1] to [4] , wherein the slag component adjusting agent has an Ig.Loss amount of 15 to 35% by mass. .
本発明の溶融金属の精錬方法によれば、精錬容器に投入されるスラグ成分調整剤は、炉内温度でガスを発生させるガス発生物質を含むため溶解性が高く、炉に投入した際に速やかに溶解して内張り耐火物の溶損を効果的に抑制することができるとともに、炉に投入した際に、ガス発生物質（Ａ）からのガス発生（例えば、Ｍｇ（ＯＨ）２からのＨ２Ｏの乖離）とガス発生物質（Ｂ）からのガス発生（例えば、ＭｇＣＯ３からのＣＯ２の乖離）が時間差をもって生じるため、ガス（例えば、Ｈ２Ｏ、ＣＯ２）の発生が穏やかになり、炉口からの急激なガス吹き出しを防止することができる。 According to the molten metal refining method of the present invention, the slag component adjusting agent charged into the refining vessel contains a gas generating substance that generates gas at the furnace temperature, and thus has high solubility, and when it is charged into the furnace, erosion it is possible to effectively suppress the dissolution to refractory lining, when charged into the furnace, the gas generated from the gas generating material (a) (eg, H 2 from Mg (OH) 2 O) and gas generation from the gas generating substance (B) (for example, CO 2 from MgCO 3 ) occur with a time difference, so that the generation of gas (for example, H 2 O, CO 2 ) becomes gentle. A sudden gas blow-out from the furnace port can be prevented.
本発明の溶融金属の精錬方法は、ＭｇＯを主体とする内張り耐火物を備えた精錬容器にて溶融金属の精錬を行う方法であり、Ｍｇ含有原料を主材とする粉粒状原料を成形し、固化させた成形体であって、ガス発生温度が４００℃以下であるガス発生物質Ａとガス発生温度が６００℃以上であるガス発生物質Ｂを含有するスラグ成分調整剤を、精錬容器に投入して溶融金属の精錬を行うものである。ここで、ガス発生物質とは、加熱されることで熱分解を生じ、ガスが発生（乖離）する物質を指す。
このようなスラグ成分調整剤は、ガス発生物質Ａ，Ｂを含むため溶解性が高く、炉に投入した際に速やかに溶解するとともに、ガス発生物質Ａからのガス発生とガス発生物質Ｂからのガス発生が時間差をもって生じるため、ガスの発生が穏やかになる利点がある。
本発明が適用される溶融金属の精錬は、ＭｇＯを主体とする内張り耐火物を備えた精錬容器にて行われる精錬であれば特別な制限はなく、鉄鋼以外の金属の精錬プロセスにも適用できる。また、鉄鋼製造プロセスの場合には、製鋼プロセスである転炉脱炭精錬や溶銑予備処理での精錬（例えば、脱硫処理、脱燐処理など）、溶融還元精錬などに適用できる。
The molten metal refining method of the present invention is a method of refining molten metal in a refining vessel equipped with a lining refractory mainly composed of MgO, molding a granular raw material mainly composed of a Mg-containing raw material, A slag component adjusting agent containing a gas generating material A having a gas generation temperature of 400 ° C. or lower and a gas generating material B having a gas generation temperature of 600 ° C. or higher is charged into a refining vessel. In this way, molten metal is refined. Here, the gas generating substance refers to a substance that generates heat (dissociates) by being thermally decomposed when heated.
Since such a slag component modifier contains gas generating substances A and B, it has high solubility, and when it is put into the furnace, it dissolves quickly, and the gas generation from the gas generating substance A and the gas generating substance B Since the gas generation occurs with a time difference, there is an advantage that the gas generation becomes gentle.
The refining of molten metal to which the present invention is applied is not particularly limited as long as it is performed in a refining vessel equipped with a refractory mainly composed of MgO, and can be applied to a refining process of metals other than steel. . In the case of a steel manufacturing process, it can be applied to converter decarburization refining, refining in hot metal preliminary treatment (for example, desulfurization treatment, dephosphorization treatment, etc.), smelting reduction refining and the like.
以下、本発明で使用するスラグ成分調整剤について説明する。
粉粒状原料を成形体とするのは、粉粒状原料のまま炉に投入すると、炉から発生するガス中に飛散してしまうからである。粉粒状原料（特に、Ｍｇ含有原料）は、溶解性を確保するために粒径１０ｍｍ以下のものが好ましい。
通常、スラグ成分調整剤を構成する成形体は、バインダーとして水または／および有機物質などを加えて混練した粉粒状原料を成形し、固化させることにより得られる。このように水や有機物質などのバインダーで固形化することにより、炉に投入した際の粉化（崩壊）性が高くなり、より優れた溶解性が得られる。
バインダーとなる有機物質としては、例えば、例えば、澱粉、タール系物質、ピッチ系物質などが挙げられ、これらの１種以上を用いることができる。このような有機物質も、高温に加熱されると分解してＣＯ２やＨ２Ｏなどのガスを発生させるので、ガス発生物質Ａまたはガス発生物質Ｂとして機能する場合がある。
Hereinafter, the slag component adjusting agent used in the present invention will be described.
The reason why the powdery raw material is formed into a compact is that if the powdery raw material is put into the furnace as it is, it will be scattered in the gas generated from the furnace. The granular raw material (particularly Mg-containing raw material) preferably has a particle diameter of 10 mm or less in order to ensure solubility.
Usually, the molded object which comprises a slag component regulator is obtained by shape | molding and solidifying the granular raw material knead | mixed by adding water or / and an organic substance etc. as a binder. Thus, by solidifying with binders, such as water and an organic substance, the powdering (disintegration) property at the time of throwing into a furnace becomes high, and more excellent solubility is obtained.
As an organic substance used as a binder, starch, a tar type material, a pitch type material etc. are mentioned, for example, One or more types of these can be used. Such an organic substance also decomposes when heated to a high temperature to generate a gas such as CO 2 or H 2 O, and thus may function as the gas generating substance A or the gas generating substance B.
本発明で使用するスラグ成分調整剤は、Ｍｇ含有原料を主材とする粉粒状原料から得られるものであるので、ガス発生物質ＡとしてはＭｇ（ＯＨ）２が、ガス発生物質ＢとしてはＭｇＣＯ３が、それぞれ好適であり、特に、スラグ成分調整剤はＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２を主成分とすることが好ましい。
Ｍｇ（ＯＨ）２は２５０〜３００℃程度でＨ２Ｏが乖離するため、ＭｇＯとＭｇ（ＯＨ）２を主成分とするスラグ成分調整剤の場合には、炉に投入すると直ぐにＭｇ（ＯＨ）２からＨ２Ｏが乖離し、炉口からの急激なガス吹き出しを生じてしまう。これに対して、ＭｇＣＯ３は６００〜７００℃まで昇熱しないとＣＯ２が乖離しないので、スラグ成分調整剤が、上記のようにガス発生物質ＡとしてＭｇ（ＯＨ）２を、ガス発生物質ＢとしてＭｇＣＯ３をそれぞれ含有する場合（特に好ましくは、ＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２を主成分とする場合）には、炉に投入した際にＭｇ（ＯＨ）２からのＨ２Ｏの乖離と、ＭｇＣＯ３からのＣＯ２の乖離が時間差をもって生じ、この結果、ガス（Ｈ２Ｏ、ＣＯ２）の発生が穏やかになり、炉口からの急激なガス吹き出しを抑えることができる。
Since the slag component modifier used in the present invention is obtained from a granular raw material mainly composed of an Mg-containing raw material, Mg (OH) 2 is used as the gas generating material A, and MgCO is used as the gas generating material B. 3 is preferable, and it is particularly preferable that the slag component modifier is composed mainly of MgO, MgCO 3 and Mg (OH) 2 .
Since Mg (OH) 2 is separated from H 2 O at about 250 to 300 ° C., in the case of a slag component modifier mainly composed of MgO and Mg (OH) 2 , Mg (OH) is immediately put into the furnace. 2 H 2 O is deviated from, it occurs a blowoff rapid gas from the furnace opening. In contrast, since the MgCO 3 is Without Noborinetsu CO 2 does not deviate to 600 to 700 ° C., the slag component modifier, the Mg (OH) 2 as the gas generating substance A as described above, the gas generating material B Each containing MgCO 3 (particularly preferably, MgO, MgCO 3 and Mg (OH) 2 as main components), when H 2 O from Mg (OH) 2 is introduced into the furnace. The deviation and the deviation of CO 2 from MgCO 3 occur with a time difference. As a result, the generation of gas (H 2 O, CO 2 ) becomes gentle, and a rapid gas blow-out from the furnace port can be suppressed.
ここで、ＭｇＯ源、Ｍｇ（ＯＨ）２源となる粉粒状原料としては、軽焼マグネシア、マグネシアクリンカー、軽焼ドロマイトなどが挙げられ、これらの１種以上を用いることができる。また、ＭｇＣＯ３源となる粉粒状原料としては、マグネサイト、生ドロマイトなどが挙げられ、これらの１種以上を用いることができる。
スラグ成分調整剤に含まれるＭｇ（ＯＨ）２は、元々その成分の原料として配合されたものでもよいが、通常は、原料であるＭｇＯの一部が水和（大気中の水分、製造時に添加される水などによる水和）することで生成したものである。
Here, as a granular raw material used as a MgO source and a Mg (OH) 2 source, a light-burning magnesia, a magnesia clinker, a light-burning dolomite, etc. are mentioned, 1 or more types of these can be used. As the particulate material becomes MgCO 3 source, magnesite, etc. raw dolomite and the like, can be used one or more of these.
Mg (OH) 2 contained in the slag component modifier may be originally blended as a raw material of the component, but usually a part of the raw material MgO is hydrated (water in the atmosphere, added during production) Hydrated with water or the like).
本発明で使用するスラグ成分調整剤がＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２を主成分とする場合、含有するＭｇ化合物中での割合で、ＭｇＯ含有量が３５〜８０質量％、ＭｇＣＯ３含有量が１５〜５０質量％、Ｍｇ（ＯＨ）２含有量が５〜４０質量％であることが好ましい。
ＭｇＯ含有量が３５質量％未満では、相対的にＭｇＣＯ３とＭｇ（ＯＨ）２の含有量が高くなる結果、ガス発生量が全体的に過剰になるとともに、ＭｇＯの絶対量が不足するため、内張り耐火物の溶損が進行しやすい。一方、８０質量％を超えると、相対的にＭｇＣＯ３とＭｇ（ＯＨ）２の含有量が少なくなるためにガス発生量が不足し、成形体の粉化（崩壊）性が低下し、溶解性が不十分となりやすい。
When the slag component modifier used in the present invention is mainly composed of MgO, MgCO 3 and Mg (OH) 2 , the MgO content is 35 to 80% by mass and the MgCO 3 content is a ratio in the contained Mg compound. The amount is preferably 15 to 50% by mass, and the Mg (OH) 2 content is preferably 5 to 40% by mass.
When the content of MgO is less than 35% by mass, the content of MgCO 3 and Mg (OH) 2 is relatively high. As a result, the gas generation amount becomes excessive as a whole, and the absolute amount of MgO is insufficient. Erosion of lining refractories tends to progress. On the other hand, if it exceeds 80% by mass, the content of MgCO 3 and Mg (OH) 2 is relatively reduced, so that the amount of gas generation is insufficient, and the powdered (collapse) property of the molded product is lowered, so that the solubility is reduced. Tends to be insufficient.
また、ＭｇＣＯ３含有量が１５質量％未満では、ガス発生物質ＢとしてＭｇＣＯ３を含有させることによる本発明の効果が低下する。一方、ＭｇＣＯ３含有量が５０質量％を超えると、ＭｇＣＯ３から発生するＣＯ２によるガス吹き出しの問題が大きくなるとともに、ＭｇＯの絶対量が少なくなるので、内張り耐火物の溶損が進行しやすい。また、以上の観点から、より好ましいＭｇＣＯ３含有量は３０〜５０質量％である。
また、Ｍｇ（ＯＨ）２含有量が５質量％未満ではＭｇ（ＯＨ）２から発生するＨ２Ｏガスが不足し、成形体の粉化（崩壊）が低下し、溶解性が不十分となりやすい。一方、Ｍｇ（ＯＨ）２含有量が４０質量％を超えると、Ｍｇ（ＯＨ）２から発生するＨ２Ｏガスによるガス吹き出しの問題が大きくなるとともに、ＭｇＯの絶対量が少なくなるので、内張り耐火物の溶損が進行しやすい。
On the other hand, when the MgCO 3 content is less than 15% by mass, the effect of the present invention by containing MgCO 3 as the gas generating substance B is lowered. On the other hand, if the MgCO 3 content exceeds 50% by mass, the problem of gas blowing due to CO 2 generated from MgCO 3 increases, and the absolute amount of MgO decreases, so that the refractory of the lining refractory tends to progress. . From the above viewpoint, the more preferable MgCO 3 content is 30 to 50% by mass.
In addition, if the Mg (OH) 2 content is less than 5% by mass, the H 2 O gas generated from Mg (OH) 2 is insufficient, and the powdered (collapsed) shape of the molded product is reduced, so that the solubility tends to be insufficient. . On the other hand, if the Mg (OH) 2 content exceeds 40% by mass, the problem of gas blowing by H 2 O gas generated from Mg (OH) 2 increases, and the absolute amount of MgO decreases, so the lining fire resistance The erosion of objects tends to progress.
ＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２からなるスラグ成分調整剤であって、ＭｇＣＯ３含有量を種々変化させたスラグ成分調整剤（ＭｇＣＯ３含有量：０質量％のものを含む）を製造し、これらを吹錬中の転炉に投入し、スラグ成分調整剤のＭｇＣＯ３含有量と発生ガスの吹き出し状況との関係を調べた。なお、スラグ成分調整剤中のＭｇＯ含有量とＭｇ（ＯＨ）２含有量は、それぞれ０〜６０質量％、０〜４０質量％とした。
図１は、その結果を示すもので、縦軸は転炉に投入したスラグ成分調整剤から発生するガス（Ｈ２Ｏ，ＣＯ２）の吹き出し状況を指数化した吹出指数であり、この値が大きいほど炉口からのガス吹き出しの程度が大きく、好ましくないことを示している。吹出指数の評価は以下のとおりである。
４：吹錬中止レベル
３：送酸速度ダウンレベル
２：地金付着レベル（操業条件変更不要）
１：問題なし
MgO, a slag component modifier consisting of MgCO 3 and Mg (OH) 2, MgCO 3 content of various altered so slag component modifier (MgCO 3 content: 0 include those of mass%) to prepare a These were introduced into the converter during blowing, and the relationship between the MgCO 3 content of the slag component modifier and the state of blowing out the generated gas was investigated. In addition, MgO content and Mg (OH) 2 content in a slag component regulator were 0-60 mass% and 0-40 mass%, respectively.
FIG. 1 shows the result, and the vertical axis represents the blowing index obtained by indexing the blowing state of the gas (H 2 O, CO 2 ) generated from the slag component modifier charged in the converter. The larger the value, the greater the degree of gas blowing from the furnace port, which is not preferable. The blowout index is evaluated as follows.
4: Blowing cancellation level 3: Acid feed rate down level 2: Metal adhesion level (no change in operating conditions)
1: No problem
図１によると、スラグ成分調整剤がＭｇＣＯ３を含まない場合には、発生ガスはすべてＭｇ（ＯＨ）２からのＨ２Ｏであり、炉に投入して直ぐに大量のＨ２Ｏが発生するのでガス吹き出しが大きく、吹出指数が高い。これに対して、ＭｇＣＯ３が配合されると、発生ガスの一部がＭｇＣＯ３から発生するＣＯ２に置き換わり、しかも乖離温度の違いからＣＯ２はＨ２Ｏよりも遅れて発生するため、含有するＭｇＣＯ３がある程度の比率になると、ガスの発生が平均化して穏やかになり、吹出指数は小さくなる。具体的には、ＭｇＣＯ３含有量が１５質量％以上において、その効果が顕在化し、特に３０質量％以上において最も効果が大きくなる。 According to FIG. 1, when the slag component modifier does not contain MgCO 3 , the generated gas is all H 2 O from Mg (OH) 2 , and a large amount of H 2 O is generated immediately after being introduced into the furnace. Therefore, the gas blowout is large and the blowout index is high. On the other hand, when MgCO 3 is blended, part of the generated gas is replaced with CO 2 generated from MgCO 3 , and CO 2 is generated later than H 2 O due to the difference in the dissociation temperature. When the ratio of MgCO 3 to be reached becomes a certain ratio, the generation of gas is averaged and becomes milder, and the blowing index becomes smaller. Specifically, when the MgCO 3 content is 15% by mass or more, the effect becomes obvious, and particularly when the MgCO 3 content is 30% by mass or more, the effect is greatest.
本発明で使用するスラグ成分調整剤は、Ig.Loss量が１５〜３５質量％であることが好ましい。ここで、Ig.Loss量とは１０００℃に加熱して失われる揮発成分の質量％を指す。炉に投入されたスラグ成分調整剤がその機能を速やかに発揮するには、スラグ成分調整剤の成形体が速やかに崩壊・粉化し、スラグに溶解することが必要である。炉に投入された成形体はそれ自体の発生ガス（Ｍｇ（ＯＨ）２から発生するＨ２Ｏ、ＭｇＣＯ３から発生するＣＯ２）によって崩壊・粉化することが好ましく、したがって、スラグ成分調整剤にはある程度のIg.Lossがあった方がよい。スラグ成分調整剤のIg.Loss量が１５質量％未満では、発生ガスによるスラグ成分調整剤の崩壊・粉化が進みにくい。一方、スラグ成分調整剤のIg.Loss量が多くなると、発生ガスによるスラグ成分調整剤の崩壊・粉化は進むが、スラグ成分調整剤の構成成分のＭｇＯ濃度（ＭｇＯ換算濃度）が低くなるので効率が悪くなり、特に３５質量％を超えると、後述するような有効ＭｇＯ濃度指数が十分でなくなる。また、以上の観点からより好ましいIg.Loss量は１５〜２５質量％である。 As for the slag component regulator used by this invention, it is preferable that the amount of Ig.Loss is 15-35 mass%. Here, the amount of Ig.Loss refers to the mass% of the volatile component lost by heating to 1000 ° C. In order for the slag component adjusting agent charged in the furnace to exhibit its function quickly, it is necessary that the molded body of the slag component adjusting agent rapidly disintegrate / pulverize and dissolve in the slag. It is preferable that the molded body put into the furnace is disintegrated and pulverized by its own generated gas (H 2 O generated from Mg (OH) 2 , CO 2 generated from MgCO 3 ). Should have some Ig.Loss. When the Ig.Loss amount of the slag component modifier is less than 15% by mass, the slag component modifier is not easily disintegrated or powdered by the generated gas. On the other hand, when the amount of Ig.Loss of the slag component modifier increases, the slag component modifier is disintegrated and powdered by the generated gas, but the MgO concentration (MgO equivalent concentration) of the constituent components of the slag component modifier decreases. If the efficiency is deteriorated, particularly exceeding 35% by mass, an effective MgO concentration index as will be described later becomes insufficient. Further, from the above viewpoint, the more preferable amount of Ig.Loss is 15 to 25% by mass.
ＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２からなるスラグ成分調整剤であって、Ig.Loss量を種々変化させたスラグ成分調整剤を製造し、これらを吹錬中の転炉に投入し、スラグ成分調整剤中のIg.Loss量がスラグ成分調整剤の機能に及ぼす影響を調べた。なお、スラグ成分調整剤中のＭｇＯ含有量、ＭｇＣＯ３含有量、Ｍｇ（ＯＨ）２含有量は、それぞれ０〜１００質量％、０〜６０質量％、０〜４０質量％とした。
図２は、その結果を示すもので、縦軸は転炉に投入したスラグ成分調整剤のＭｇＯが溶解して有効に機能したかどうかを指数化した「有効ＭｇＯ指数」であり、この値が大きいほど好ましい。図２によると、スラグ成分調整剤中のIg.Loss量が少なすぎると、発生ガスによるスラグ成分調整剤の崩壊・粉化が進みにくいので、有効ＭｇＯ指数は低い。これに対してスラグ成分調整剤のIg.Loss量が１５質量％以上となると、有効ＭｇＯ指数は十分に高いレベルになる。
A slag component adjuster comprising MgO, MgCO 3 and Mg (OH) 2 , which is produced by varying the amount of Ig.Loss, and is introduced into a converter during blowing to produce slag The effect of the amount of Ig.Loss in the component modifier on the function of the slag component modifier was investigated. Incidentally, MgO content in the slag component modifier, MgCO 3 content, Mg (OH) 2 content is 0 to 100 wt%, respectively, 0 to 60 wt%, and 0 to 40 wt%.
FIG. 2 shows the result, and the vertical axis is an “effective MgO index” obtained by indexing whether or not the MgO of the slag component modifier charged into the converter has dissolved and functioned effectively. Larger is preferable. According to FIG. 2, if the amount of Ig.Loss in the slag component modifier is too small, the effective MgO index is low because the slag component modifier is not easily disintegrated and powdered by the generated gas. On the other hand, when the amount of Ig.Loss of the slag component modifier is 15% by mass or more, the effective MgO index becomes a sufficiently high level.
図３は、図２の有効ＭｇＯ指数と、スラグ成分調整剤の構成成分のＭｇＯ換算濃度（＝［％ＭｇＯ］＋［％Ｍｇ（ＯＨ）２］×０．６７＋［％ＭｇＣＯ３］×０．４７）との積を「有効ＭｇＯ濃度」として求め、この有効ＭｇＯ濃度とスラグ成分調整剤中のIg.Loss量との関係を示したものである。この有効ＭｇＯ濃度は、スラグ中に溶解したＭｇＯ濃度を示すもので、この値が大きいほど溶解が良好であることを示す。図３によると、スラグ成分調整剤のIg.Loss量：約２０質量％を境として、それ以下の領域ではIg.Loss量が多いほど有効ＭｇＯ濃度は高くなるが、Ig.Loss量：約２０質量％超の領域では、有効ＭｇＯ指数（図２）は高いものの、スラグ成分調整剤の構成成分のＭｇＯ換算濃度が低くなることにより、有効ＭｇＯ濃度は低下に転じ、Ig.Loss量が多いほど有効ＭｇＯ濃度は低くなる。具体的には、Ig.Loss量が１５〜３５質量％では有効ＭｇＯ濃度は十分高いレベルになり、特に１５〜２５質量％が最も高いレベルになる。 FIG. 3 shows the effective MgO index of FIG. 2 and the MgO equivalent concentration (= [% MgO] + [% Mg (OH) 2 ] × 0.67 + [% MgCO 3 ] × 0. 47) is obtained as “effective MgO concentration”, and the relationship between this effective MgO concentration and the amount of Ig.Loss in the slag component adjusting agent is shown. This effective MgO concentration indicates the MgO concentration dissolved in the slag, and the larger this value, the better the dissolution. According to FIG. 3, the amount of Ig.Loss of the slag component modifier: about 20% by mass as a boundary, the effective MgO concentration increases as the amount of Ig.Loss increases, but the amount of Ig.Loss: about 20 In the region exceeding mass%, the effective MgO index (FIG. 2) is high, but as the MgO equivalent concentration of the constituent component of the slag component modifier decreases, the effective MgO concentration starts to decrease, and the greater the amount of Ig. The effective MgO concentration is lowered. Specifically, when the amount of Ig.Loss is 15 to 35% by mass, the effective MgO concentration is sufficiently high, and particularly 15 to 25% by mass is the highest level.
スラグ成分調整剤は、さらに、ＣａＣＯ３を含有することができる。このＣａＣＯ３は、６００〜７００℃程度でＣＯ２を乖離するのでガス発生物質Ｂとして機能し、また、ＣａＣＯ３を含有することによりスラグ塩基度の調整も可能となる。
ＣａＣＯ３含有量は１０mass％以下が好ましい。ＣａＣＯ３含有量が１０mass％超えるとＭｇＯの絶対量が不足するために、内張り耐火物の溶損が進行しやすい。
以上のように本発明で使用するスラグ成分調整剤は、好ましくはＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２を主成分とし、必要に応じてＣａＣＯ３を含有するものである。このようなスラグ成分調整剤は、炉に投入された際にその構成成分からＣＯ２、Ｈ２Ｏガスが発生（乖離）し、このガスにより成形体が崩壊・粉化してスラグ中に分散され、速やかに溶解する。
The slag component adjusting agent can further contain CaCO 3 . This CaCO 3 functions as a gas generating substance B because it dissociates CO 2 at about 600 to 700 ° C., and the slag basicity can be adjusted by containing CaCO 3 .
The CaCO 3 content is preferably 10 mass% or less. When the CaCO 3 content exceeds 10 mass%, the absolute amount of MgO is insufficient, so that the lining refractory tends to melt.
As described above, the slag component adjusting agent used in the present invention is preferably composed mainly of MgO, MgCO 3 and Mg (OH) 2 and contains CaCO 3 as necessary. When such a slag component modifier is introduced into the furnace, CO 2 and H 2 O gas are generated (dissociated) from the constituent components, and the molded body is disintegrated and powdered by this gas and dispersed in the slag. Dissolves quickly.
次に、以上のようなスラグ成分調整剤の好ましい製造方法について説明する。
この製造方法では、少なくともＭｇＯとＭｇＣＯ３を含む粉粒状原料にバインダーを加えて混練し、この混練物を成形した後、固化させる。
バインダーとしては、水または／および有機物質が適している。有機物質としては、さきに述べたように、例えば、澱粉、タール系物質、ピッチ系物質などが挙げられ、これらの１種以上を用いることができる。
水をバインダーとする場合には、ＭｇＯの水和硬化により成形体が固化する。スラグ成分調整剤のＭｇ（ＯＨ）２含有量は、粉粒状原料の元々の水分量やバインダーとして添加する水の量などにより、調整可能である。
Next, the preferable manufacturing method of the above slag component regulators is demonstrated.
In this manufacturing method, a binder is added to a granular raw material containing at least MgO and MgCO 3 and kneaded, and the kneaded product is molded and then solidified.
Water or / and organic substances are suitable as the binder. Examples of the organic material include starch, tar-based material, pitch-based material, and the like as described above, and one or more of these can be used.
When water is used as a binder, the molded body is solidified by hydration hardening of MgO. The Mg (OH) 2 content of the slag component adjusting agent can be adjusted by the original moisture content of the granular raw material, the amount of water added as a binder, and the like.
粉粒状原料として使用できるＭｇＯ源、ＭｇＣＯ３源は、さきに述べたとおりである。具体的な製造条件としては、例えば、軽焼ドロマイトなどのＭｇＯ源：３５〜８０質量％、軽焼マグネシアなどのＭｇＣＯ３源：２０〜５０質量％を配合し（さらに、必要に応じて他の粉粒状原料を適量配合する）、この粉粒状原料に対して、バインダーである水を１０〜２０質量％加えて混錬し、この混練物を型などを用いて成形する。この成形体を適当に養生して固化させる。これにより、所定の含有量のＭｇＯ、ＭｇＣＯ３およびＭｇ（ＯＨ）２を主成分とする本発明のスラグ成分調整剤を得ることができる。 The MgO source and MgCO 3 source that can be used as the powdery raw material are as described above. As specific production conditions, for example, MgO source such as light-burned dolomite: 35 to 80% by mass, MgCO 3 source such as light-burned magnesia: 20 to 50% by mass (in addition, if necessary, other An appropriate amount of the granular raw material is blended), and 10 to 20% by mass of water as a binder is added to the granular raw material and kneaded, and the kneaded product is molded using a mold or the like. This molded body is appropriately cured and solidified. This makes it possible to obtain a predetermined MgO content, the slag component modifier of the present invention composed mainly of MgCO 3 and Mg (OH) 2.
焼ＭｇＯ、ＭｇＣＯ３の粉粒状原料を用い、これらの粉粒状原料にバインダーである水を加えて混練し、この混練物を型を用いて成形し、表１に示す成分組成とIg.Loss量のスラグ成分調整剤を製造した。
このスラグ成分調整剤を転炉脱炭吹錬において炉内に投入し、スラグ成分調整剤から発生するガス（Ｈ２Ｏ，ＣＯ２）の吹き出し状況、スラグ成分調整剤による炉体内張り耐火物の溶損抑制効果を調べた。その結果を表１に併せて示す。スラグ成分調整剤から発生するガスの吹き出し状況は、図１と同じ吹出指数で評価した。また、炉体内張り耐火物の溶損抑制効果は、有効ＭｇＯ濃度（＝［ＭｇＯ濃度（x）］×［有効ＭｇＯ指数（y）］）に応じて、下記の評価基準で評価した。
◎：有効ＭｇＯ濃度６５mass％以上
○：有効ＭｇＯ濃度５０mass％以上、６５mass％未満
×：有効ＭｇＯ濃度５０mass％未満
Using powdered raw materials of baked MgO and MgCO 3 , water as a binder is added to these powdered raw materials and kneaded. The kneaded product is molded using a mold, and the component composition and Ig.Loss amount shown in Table 1 are used. The slag component modifier was manufactured.
This slag component modifier is put into the furnace in the converter decarburization blowing, and the gas (H 2 O, CO 2 ) blowing state generated from the slag component modifier, The melting loss suppressing effect was investigated. The results are also shown in Table 1. The blowing state of the gas generated from the slag component adjusting agent was evaluated using the same blowing index as in FIG. Further, the melting damage suppressing effect of the furnace refractory was evaluated according to the following evaluation criteria according to the effective MgO concentration (= [MgO concentration (x)] × [effective MgO index (y)]).
◎: Effective MgO concentration of 65 mass% or more ○: Effective MgO concentration of 50 mass% or more and less than 65 mass% ×: Effective MgO concentration of less than 50 mass%
Claims (5)
Ｍｇ含有原料を主材とする粉粒状原料を成形し、固化させた成形体であって、ＭｇＯ、ＭｇＣＯ ３ およびＭｇ（ＯＨ） ２ を主成分とするスラグ成分調整剤を、精錬容器に投入して溶融金属の精錬を行うことを特徴とする溶融金属の精錬方法。 In a method of refining molten metal in a refining vessel equipped with a refractory lining mainly composed of MgO,
A shaped product obtained by molding and solidifying a powdery raw material mainly composed of an Mg-containing raw material, and introducing a slag component modifier mainly composed of MgO, MgCO 3 and Mg (OH) 2 into a refining vessel A method for refining molten metal, comprising refining molten metal.
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| PL2813481T3 (en) * | 2013-06-10 | 2015-10-30 | Refractory Intellectual Property Gmbh & Co Kg | Formulation for producing an unshaped refractory ceramic product, method for the preparation of a fired refractory ceramic product, a fired refractory ceramic product as well as the use of an unshaped refractory ceramic product |
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