JP5482540B2 - Hot metal desulfurization method - Google Patents
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Description
本発明は、ＣａＯとＭｇＯを主成分とする精錬剤を用いて行う溶銑の脱硫において、溶銑中にＡｌを添加し、脱硫能の低下を抑制する脱硫方法に関する。 The present invention relates to a desulfurization method in which Al is added to hot metal to suppress a decrease in desulfurization ability in desulfurization of hot metal performed using a refining agent mainly composed of CaO and MgO.
溶銑の脱硫処理においては、ＣａＯに金属Ｍｇを混合した精錬剤を用いると、高い脱硫能が得られることが一般的に知られている。これは、ＣａＯによる脱硫に加えて、Ｍｇ蒸気による脱硫が起こるためである。 In the hot metal desulfurization treatment, it is generally known that a high desulfurization ability can be obtained by using a refining agent in which metallic Mg is mixed with CaO. This is because desulfurization with Mg vapor occurs in addition to desulfurization with CaO.
しかし、金属Ｍｇは、ＣａＯに比べ高価であり、金属Ｍｇを使用すると、脱硫コストが増加する。それ故、高価な金属Ｍｇを含まず、脱硫能の高い精錬剤が求められている。 However, metallic Mg is more expensive than CaO, and the use of metallic Mg increases the desulfurization cost. Therefore, there is a need for a refining agent that does not contain expensive metal Mg and has a high desulfurization ability.
このような要望に応える手段の一つとして、特許文献１に、Ａｌ、ＭｇＯ及びＣａＯを主成分とする精錬剤を用いる精錬方法が開示されている。この精錬方法においては、精錬剤を溶鉄中に供給すると、溶鉄中でＭｇ蒸気が生成し、そのＭｇ蒸気により精錬反応が進行する。 As one means for meeting such a demand, Patent Document 1 discloses a refining method using a refining agent mainly composed of Al, MgO, and CaO. In this refining method, when a refining agent is supplied into molten iron, Mg vapor is generated in the molten iron, and the refining reaction proceeds by the Mg vapor.
また、特許文献２には、金属Ａｌを５〜３０質量％とし、金属Ｍｇ又はＭｇＯ、ＣａＯを混合した粒状及び／又は粉状の脱硫剤を鉄系帯材で被覆した鉄被覆脱硫用ワイヤーを溶銑中に供給して脱硫処理を行う溶銑の脱硫方法が開示されている。 Patent Document 2 discloses an iron-coated desulfurization wire in which metal Al is 5 to 30% by mass, and a granular and / or powdery desulfurization agent mixed with metal Mg or MgO and CaO is coated with an iron-based strip. A hot metal desulfurization method in which desulfurization is performed by supplying the hot metal into hot metal is disclosed.
しかし、特許文献１記載の精錬方法においては、ＭｇＯが還元されＭｇ蒸気が生成するように、溶鋼中のＡｌ量を０．０１質量％以上と規定しているが、本発明者らは、Ａｌ濃度が高すぎると、脱硫能が低下することを確認した。特許文献２記載の溶銑の脱硫処理方法においては、溶銑中のＡｌ濃度は規定されていない。 However, in the refining method described in Patent Document 1, the amount of Al in the molten steel is defined as 0.01% by mass or more so that MgO is reduced and Mg vapor is generated. It was confirmed that when the concentration was too high, the desulfurization ability decreased. In the hot metal desulfurization treatment method described in Patent Document 2, the Al concentration in the hot metal is not specified.
そこで、本発明者らは、溶銑中のＡｌ濃度が、脱硫に大きく影響すると考え、本発明においては、ＣａＯとＭｇＯを主成分とする精錬剤を用いて溶銑を脱硫する際、溶銑にＡｌを添加して、Ａｌ濃度を適正範囲に制御し、脱硫能の低下を抑制することを課題とし、該課題を解決する脱硫方法を提供することを目的とする。 Therefore, the present inventors consider that the Al concentration in the hot metal greatly affects desulfurization, and in the present invention, when desulfurizing the hot metal using a refining agent mainly composed of CaO and MgO, Al is added to the hot metal. It is an object to provide a desulfurization method that solves the problem by adding and controlling the Al concentration within an appropriate range to suppress a decrease in desulfurization ability.
本発明者らは、溶銑中のＡｌ濃度の適正範囲を鋭意調査した。その結果、溶銑中のＡｌ濃度を０．００５〜０．１％に調整すれば、溶銑中におけるカルシューム−アルミネートの生成が抑制されて、脱硫能が低下しないことを見いだした。 The inventors diligently investigated the appropriate range of Al concentration in the hot metal. As a result, it has been found that if the Al concentration in the hot metal is adjusted to 0.005 to 0.1%, the formation of calcium aluminate in the hot metal is suppressed and the desulfurization ability does not decrease.
本発明は、上記知見に基づいてなされたもので、その要旨は以下の通りである。 The present invention has been made based on the above findings, and the gist thereof is as follows.
（１）溶銑の脱硫方法において、精錬剤として、焼成ドロマイト、あるいは焼成ドロマイトに石灰、ＭｇＯ系耐火物、焼成ブルーサイトのいずれか１種又は２種以上を混合したものを用い、該精錬剤を、Ａｌ濃度を０．００５〜０．１質量％に調整した溶銑中に吹き込むか、又は、前記溶銑の上方から添加して攪拌することを特徴とする溶銑の脱硫方法。
(1) in the de vulcanizing method molten iron, used as a refining agent, lime calcined dolomite or calcined dolomite,, MgO-based refractory, a mixture of any one or two or more of the firing brucite, the A hot metal desulfurization method , wherein a refining agent is blown into hot metal having an Al concentration adjusted to 0.005 to 0.1% by mass , or added from above the hot metal and stirred .
（２）前記Ａｌ濃度を調整するＡｌの原料として、金属Ａｌ及びＡｌドロスのいずれか１種又は２種を用いることを特徴とする前記（１）に記載の溶銑の脱硫方法。 (2) The hot metal desulfurization method according to (1), wherein any one or two of metal Al and Al dross is used as an Al raw material for adjusting the Al concentration.
本発明によれば、溶銑の脱硫において、高い脱硫能を維持して脱硫を促進することができる。 According to the present invention, desulfurization of hot metal can promote desulfurization while maintaining high desulfurization ability.
本発明者らは、溶銑脱硫において高い脱硫能を持つ金属ＭｇのＭｇ源として、ＭｇＯに着目した。そして、ＣａＯとＭｇＯを主成分とする精錬剤を溶銑に吹込んで脱硫を行う際、ＭｇＯを還元して高脱硫能を得ることができる溶銑のＡｌ濃度を調査した。その結果を、図１に示す。
The present inventors paid attention to MgO as a Mg source of metallic Mg having high desulfurization ability in hot metal desulfurization. Then, when desulfurization was performed by blowing a refining agent mainly composed of CaO and MgO into hot metal, the concentration of Al in hot metal that can obtain high desulfurization ability by reducing MgO was investigated. The result is shown in FIG.
図１に示すように、溶銑のＡｌ濃度が０．００５質量％未満であると、Ａｌの還元効果が充分に得られず、脱硫率が低く、一方、溶銑のＡｌ濃度が０．１質量％を超えると脱硫率が大きく低下する。
As shown in FIG. 1, when the Al concentration of the hot metal is less than 0.005% by mass, the reduction effect of Al is not sufficiently obtained and the desulfurization rate is low, while the Al concentration of the hot metal is 0.1% by mass. If it exceeds 1, desulfurization rate is greatly reduced.
これらのことから、ＣａＯとＭｇＯを主成分とする精錬剤を用いて溶銑の脱硫を行う場合、溶銑のＡｌ濃度を０．００５〜０．１質量％に調整すれば、高い脱硫能を維持することができることが解る。以下、詳細を説明する。 Therefore, when hot metal desulfurization is performed using a refining agent mainly composed of CaO and MgO, high desulfurization ability is maintained by adjusting the Al concentration of the hot metal to 0.005 to 0.1% by mass. I understand that I can do it. Details will be described below.
ＣａＯとＭｇＯを主成分とする精錬剤を溶銑に添加した場合、溶銑のＡｌ濃度が０．０１質量％であると、ＭｇＯ還元が起き、脱硫が促進されることが知られている。本発明者らの試験結果においては、溶銑のＡｌ濃度が０．００５質量％でも、高い脱硫率が得られている。このことは、溶銑のＡｌ濃度が０．００５質量％でも、ＡｌによるＭｇＯの還元が起き、脱硫が促進されたと考えられる。 When a refining agent mainly composed of CaO and MgO is added to hot metal, it is known that MgO reduction occurs and desulfurization is promoted when the Al concentration of the hot metal is 0.01% by mass. In the test results of the present inventors, a high desulfurization rate is obtained even when the Al concentration of the hot metal is 0.005% by mass. This is considered that reduction of MgO by Al occurred and desulfurization was promoted even when the Al concentration of the hot metal was 0.005% by mass.
本発明者らは、溶銑のＡｌ濃度が０．１質量％を超えると脱硫率が低下する原因について調査した。 The present inventors investigated the cause of the decrease in the desulfurization rate when the Al concentration of the hot metal exceeds 0.1% by mass.
ＣａＯ／ＭｇＯ＝２の精錬剤を、Ａｌ濃度が０．０５質量％の溶銑に吹き込み、溶銑中に生成した反応物を調査した。その結果、ＣａＳとＭｇＯが隣接して存在することが判明した。また、質量比でＣａＯ／ＭｇＯ＝２の精錬剤を、Ａｌ濃度が０．１５質量％の溶銑に吹き込み、溶銑中に生成した反応物を調査した。その結果、Ｓを殆ど含まないカルシューム−アルミネートとＭｇＯが隣接して存在していることが判明した。 A refining agent of CaO / MgO = 2 was blown into hot metal having an Al concentration of 0.05% by mass, and a reaction product generated in the hot metal was investigated. As a result, it was found that CaS and MgO exist adjacent to each other. Further, a refining agent having a mass ratio of CaO / MgO = 2 was blown into hot metal having an Al concentration of 0.15% by mass, and a reaction product generated in the hot metal was investigated. As a result, it was found that calcium-aluminate containing almost no S and MgO were present adjacent to each other.
即ち、溶銑のＡｌ濃度が０．１質量％を超えると、精錬剤中のＣａＯと溶銑中のＡｌが反応して、ＭｇＯの活量を低減するカルシューム−アルミネートを生成し、その結果、脱硫率が大きく低下したと考えられる。この点が、本発明の基礎をなす知見である。 That is, when the Al concentration in the hot metal exceeds 0.1% by mass, CaO in the refining agent reacts with Al in the hot metal to produce calcium-aluminate that reduces the activity of MgO. As a result, desulfurization The rate is thought to have declined significantly. This is the knowledge forming the basis of the present invention.
本発明者らの調査においては、ＭｇＯ源として、焼成ドロマイト、焼成ブルーサイト、及び、ＭｇＯ耐火物の１種又は２種以上を用い、Ａｌ源として、金属Ａｌ又はＡｌドロスの１種又は２種を用いたが、何れも同等の脱硫率を得ることができた。 In our investigation, one or more of calcined dolomite, calcined brucite, and MgO refractory are used as the MgO source, and one or two of metal Al or Al dross is used as the Al source. In all cases, the same desulfurization rate was obtained.
焼成ドロマイトは、ドロマイト（ＣａＭｇ（ＣＯ3）2）を焼成して形成したものであり、Ｃａ分を、ＣａＯ換算で、５５〜８０質量％、Ｍｇ分を、ＭｇＯ換算で、２５〜４５質量％含有し、残部が不可避的不純物からなるものである。ドロマイトを焼成する際、焼成しすぎると、ＣａＯ粒及びＭｇＯ粒が粗大化するので、これらの粒が微細な状態で共存し得る温度でドロマイトを焼成することが好ましい。 The calcined dolomite is formed by calcining dolomite (CaMg (CO 3 ) 2 ). The Ca content is 55 to 80% by mass in terms of CaO, and the Mg content is 25 to 45% by mass in terms of MgO. It is contained, and the balance consists of inevitable impurities. When the dolomite is baked, if it is baked too much, the CaO grains and the MgO grains are coarsened. Therefore, it is preferable to fire the dolomite at a temperature at which these grains can coexist in a fine state.
焼成ブルーサイトは、ブルーサイト（Ｍｇ（ＯＨ）2）を焼成して形成したものであり、Ｍｇ分を、ＭｇＯ換算で、７５〜９５質量％含有し、残部が不可避的不純物からなるものである。ブルーサイトもドロマイトと同様に、焼成の際、焼成しすぎると、ＭｇＯ粒が粗大化するので、ＭｇＯ粒が微細な状態で維持し得る温度で焼成することが好ましい。 The calcined brucite is formed by calcining brucite (Mg (OH) 2 ), contains 75 to 95% by mass of Mg in terms of MgO, and the remainder consists of inevitable impurities. . Similarly to dolomite, brucite is also fired at a temperature at which MgO grains can be maintained in a fine state because MgO grains become coarse when fired during firing.
ＭｇＯ耐火物は、ＭｇＯ分を、ＭｇＯ換算で、８０質量％以上含有するものである。Ａｌドロスは、Ａｌを、Ａｌ換算で、３０質量％以上含有するものである。ＭｇＯ源及びＡｌ源となる原料の粒度は、反応性を考慮すると、１ｍｍ以下が好ましい。 MgO refractories contain 80% by mass or more of MgO in terms of MgO. Al dross contains 30% by mass or more of Al in terms of Al. In consideration of reactivity, the particle size of the raw material to be the MgO source and Al source is preferably 1 mm or less.
精錬剤は、溶銑中に吹き込むか、又は、上方から添加して攪拌する。溶銑がトーピードカーに収容されている場合は、精錬剤を、溶銑中に吹き込むのが好ましい。 The refining agent is blown into the hot metal or added from above and stirred. When hot metal is accommodated in the torpedo car, it is preferable to blow the refining agent into the hot metal.
（実施例１）
トーピードカーの中の溶銑（１００〜３００ton）に所定量の金属Ａｌを添加し、焼成ドロマイト（質量比でＣａＯ／ＭｇＯ＝２）を、溶銑１ton当り８ｋｇ吹き込んで脱硫処理を行った。Ａｌ添加前の溶銑は、Ｃ：４．０〜５．０質量％、Ｓｉ：０．４〜０．６質量％、及び、Ｓ：０．０２５〜０．０３５質量％を含み、溶銑温度は１４００〜１４２０℃であった。
Example 1
A predetermined amount of metal Al was added to hot metal (100 to 300 tons) in a torpedo car, and desulfurization treatment was performed by blowing 8 kg of calcined dolomite (CaO / MgO = 2 by mass) per ton of hot metal. The hot metal before the addition of Al includes C: 4.0 to 5.0 mass%, Si: 0.4 to 0.6 mass%, and S: 0.025 to 0.035 mass%, and the hot metal temperature is It was 1400-1420 degreeC.
脱硫処理前後に試料を採取し、Ｓ濃度及びＡｌ濃度を測定した。Ｓ濃度は、ＪＩＳ Ｇ １２１５（鉄及び鋼−硫黄定量方法）に従って測定し、Ａｌ濃度は、ｓol.ＡｌをＪＩＳ Ｇ １２５８（鉄及び鋼−誘導結合プラズマ発光分光分析法）で測定し、Ａｌ濃度とした。 Samples were taken before and after the desulfurization treatment, and S concentration and Al concentration were measured. S concentration is measured according to JIS G 1215 (iron and steel-sulfur determination method), Al concentration is measured by measuring sol.Al with JIS G 1258 (iron and steel-inductively coupled plasma emission spectrometry), and Al concentration. It was.
脱硫処理前後のＳ濃度から、下記式（１）に従って脱硫率（％）を計算した。 From the S concentration before and after the desulfurization treatment, the desulfurization rate (%) was calculated according to the following formula (1).
脱硫率＝（処理前Ｓ質量％−処理後Ｓ質量％）×１００／（処理前Ｓ質量％） （１）
表１に、溶銑のＡｌ濃度（質量％）と脱硫率（％）を示す。表１から、溶銑のＡｌ濃度が０．００５〜０．１％の範囲で、高い脱硫率が得られていることが解る。
Desulfurization rate = (S mass% before treatment−S mass% after treatment) × 100 / (S mass% before treatment) (1)
Table 1 shows the Al concentration (% by mass) and the desulfurization rate (%) of the hot metal. From Table 1, it is understood that a high desulfurization rate is obtained when the Al concentration of the hot metal is in the range of 0.005 to 0.1%.
（実施例２）
トーピードカーの中の溶銑（１００〜３００ton）に所定量の金属Ａｌを添加し、焼成ドロマイトとＣａＯを混合し、質量比でＣａＯ／ＭｇＯ＝４とした精錬剤を、溶銑１ton当り８ｋｇ吹き込んで脱硫処理を行った。Ａｌ添加前の溶銑は、Ｃ：４．０〜５．０質量％、Ｓｉ：０．４〜０．６質量％、及び、Ｓ：０．０２５〜０．０３５質量％を含み、溶銑温度は１４００〜１４２０℃であった。
(Example 2)
Desulfurization treatment by adding a predetermined amount of metal Al to hot metal (100 to 300 tons) in a torpedo car, mixing calcined dolomite and CaO, and blowing 8 kg of refining agent with a mass ratio of CaO / MgO = 4 per ton of hot metal Went. The hot metal before the addition of Al includes C: 4.0 to 5.0 mass%, Si: 0.4 to 0.6 mass%, and S: 0.025 to 0.035 mass%, and the hot metal temperature is It was 1400-1420 degreeC.
脱硫処理前後に試料を採取し、Ｓ濃度、及び、Ａｌ濃度を測定した。Ｓ濃度は、ＪＩＳ Ｇ １２１５（鉄及び鋼−硫黄定量方法）に従って測定し、Ａｌ濃度は、ｓol.ＡｌをＪＩＳ Ｇ １２５８（鉄及び鋼−誘導結合プラズマ発光分光分析法）で測定し、Ａｌ濃度とした。 Samples were taken before and after the desulfurization treatment, and S concentration and Al concentration were measured. S concentration is measured according to JIS G 1215 (iron and steel-sulfur determination method), Al concentration is measured by measuring sol.Al with JIS G 1258 (iron and steel-inductively coupled plasma emission spectrometry), and Al concentration. It was.
脱硫処理前後のＳ濃度から、前記式（１）に従って脱硫率（％）を計算した。 From the S concentration before and after the desulfurization treatment, the desulfurization rate (%) was calculated according to the formula (1).
表２に、溶銑のＡｌ濃度（質量％）と脱硫率（％）を示す。表２から、溶銑のＡｌ濃度が０．００５〜０．１％の範囲で、高い脱硫率が得られていることが解る。 Table 2 shows the Al concentration (% by mass) and the desulfurization rate (%) of the hot metal. From Table 2, it is understood that a high desulfurization rate is obtained when the Al concentration of the hot metal is in the range of 0.005 to 0.1%.
（実施例３）
トーピードカーの中の溶銑（１００〜３００ton）に所定量の金属Ａｌを添加し、焼成ドロマイトに、焼成ブルーサイトとＭｇＯ耐火物を１：１の日で混合したものを加えて、質量比でＣａＯ／ＭｇＯ＝１とした精錬剤を、溶銑１ton当り８ｋｇ吹き込んで脱硫処理を行った。Ａｌ添加前の溶銑は、Ｃ：４．０〜５．０質量％、Ｓｉ：０．４〜０．６質量％、及び、Ｓ：０．０２５〜０．０３５質量％を含み、溶銑温度は１４００〜１４２０℃であった。
(Example 3)
A predetermined amount of metal Al is added to hot metal (100 to 300 tons) in a torpedo car, and a mixture of calcined brucite and MgO refractory in a 1: 1 day is added to calcined dolomite, and CaO / A desulfurization treatment was performed by blowing 8 kg of a refining agent with MgO = 1 per 1 ton of hot metal. The hot metal before the addition of Al includes C: 4.0 to 5.0 mass%, Si: 0.4 to 0.6 mass%, and S: 0.025 to 0.035 mass%, and the hot metal temperature is It was 1400-1420 degreeC.
脱硫処理前後に試料を採取しＳ濃度、及び、Ａｌ濃度を測定した。Ｓ濃度は、ＪＩＳ Ｇ １２１５（鉄及び鋼−硫黄定量方法）に従って測定し、Ａｌ濃度は、ｓol.ＡｌをＪＩＳ Ｇ １２５８（鉄及び鋼−誘導結合プラズマ発行分光分析法）で測定し、Ａｌ濃度とした。 Samples were taken before and after the desulfurization treatment, and S concentration and Al concentration were measured. S concentration is measured according to JIS G 1215 (iron and steel-sulfur determination method), Al concentration is measured by measuring sol.Al with JIS G 1258 (iron and steel-inductively coupled plasma emission spectroscopy), and Al concentration. It was.
脱硫処理前後のＳ濃度から、前記式（１）に従って脱硫率（％）を計算した。 From the S concentration before and after the desulfurization treatment, the desulfurization rate (%) was calculated according to the formula (1).
表３に、溶銑のＡｌ濃度（質量％）と脱硫率（％）を示す。表３から、溶銑のＡｌ濃度が０．００５〜０．１％の範囲で、高い脱硫率が得られていることが解る。 Table 3 shows the Al concentration (% by mass) and the desulfurization rate (%) of the hot metal. From Table 3, it is understood that a high desulfurization rate is obtained when the Al concentration of the hot metal is in the range of 0.005 to 0.1%.
（実施例４）
トーピードカーの中の溶銑（１００〜３００ton）に所定量のＡｌドロスを添加し、焼成ドロマイト（質量比でＣａＯ／ＭｇＯ＝２）を、溶銑１ton当り８ｋｇ吹き込んで脱硫処理を行った。Ａｌ添加前の溶銑は、Ｃ：４．０〜５．０質量％、Ｓｉ：０．４〜０．６質量％、及び、Ｓ：０．０２５〜０．０３５質量％を含み、溶銑温度は１４００〜１４２０℃であった。
(Example 4)
A predetermined amount of Al dross was added to hot metal (100 to 300 tons) in a torpedo car, and desulfurization treatment was performed by blowing 8 kg of calcined dolomite (CaO / MgO = 2 by mass) per ton of hot metal. The hot metal before the addition of Al includes C: 4.0 to 5.0 mass%, Si: 0.4 to 0.6 mass%, and S: 0.025 to 0.035 mass%, and the hot metal temperature is It was 1400-1420 degreeC.
脱硫処理前後に試料を回収し、Ｓ濃度、及び、Ａｌ濃度を測定した。Ｓ濃度は、ＪＩＳ Ｇ １２１５（鉄及び鋼−硫黄定量方法）に従って測定し、Ａｌ濃度は、ｓol.ＡｌをＪＩＳ Ｇ １２５８（鉄及び鋼−誘導結合プラズマ発行分光分析法）で測定し、Ａｌ濃度とした。 Samples were collected before and after the desulfurization treatment, and S concentration and Al concentration were measured. S concentration is measured according to JIS G 1215 (iron and steel-sulfur determination method), Al concentration is measured by measuring sol.Al with JIS G 1258 (iron and steel-inductively coupled plasma emission spectroscopy), and Al concentration. It was.
脱硫処理前後のＳ濃度から、前記式（１）に従って脱硫率（％）を計算した。 From the S concentration before and after the desulfurization treatment, the desulfurization rate (%) was calculated according to the formula (1).
表４に、溶銑のＡｌ濃度（質量％）と脱硫率（％）を示す。表４から、Ａｌ濃度が０．００５〜０．１％の範囲で、高い脱硫率が得られていることが解る。 Table 4 shows the Al concentration (% by mass) and the desulfurization rate (%) of the hot metal. From Table 4, it is understood that a high desulfurization rate is obtained when the Al concentration is in the range of 0.005 to 0.1%.
前述したように、本発明によれば、溶銑の脱硫において、高い脱硫能を維持して脱硫を促進することができる。よって、本発明は、鉄鋼産業において利用可能性が高いものである。 As described above, according to the present invention, desulfurization of hot metal can promote desulfurization while maintaining high desulfurization ability. Therefore, the present invention has high applicability in the steel industry.
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