JP2022083582A - Steel desulfurization agent and method for manufacturing the same - Google Patents
Steel desulfurization agent and method for manufacturing the same Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 169
- 230000023556 desulfurization Effects 0.000 title claims abstract description 169
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 133
- 239000010959 steel Substances 0.000 title claims abstract description 133
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 3
- 239000002893 slag Substances 0.000 claims abstract description 61
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000460 chlorine Substances 0.000 claims abstract description 49
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 48
- 239000000292 calcium oxide Substances 0.000 claims abstract description 46
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 46
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 46
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 20
- 239000001110 calcium chloride Substances 0.000 claims description 20
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 20
- 238000010304 firing Methods 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 9
- 239000001095 magnesium carbonate Substances 0.000 claims description 9
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 4
- 239000010459 dolomite Substances 0.000 claims description 4
- 229910000514 dolomite Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 36
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000920 calcium hydroxide Substances 0.000 abstract description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 5
- 238000005660 chlorination reaction Methods 0.000 abstract 2
- 238000007670 refining Methods 0.000 abstract 1
- 235000012255 calcium oxide Nutrition 0.000 description 44
- 230000003009 desulfurizing effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007796 conventional method Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000010436 fluorite Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- CTUDRLGCNRAIEA-UHFFFAOYSA-L calcium;chloride;hydroxide Chemical compound [OH-].[Cl-].[Ca+2] CTUDRLGCNRAIEA-UHFFFAOYSA-L 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- RNDIHDKIZRODRW-UHFFFAOYSA-L magnesium;chloride;hydroxide Chemical compound [OH-].[Mg+2].[Cl-] RNDIHDKIZRODRW-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
Description
この発明は、製鉄所の高炉又は電炉から取り出される溶湯（溶銑）中に含まれる硫黄成分等の不純物を溶湯中から取り除いて鉄鋼の品質を向上させるために酸化カルシウムとともに使用される鉄鋼用脱硫助剤及びその製造方法に関する。 The present invention is a desulfurization aid for steel used together with calcium oxide to remove impurities such as sulfur components contained in molten metal (hot metal) taken out from a blast furnace or electric furnace of a steel mill from the molten metal to improve the quality of steel. The agent and its manufacturing method.
一般に鉄鋼用脱硫剤として生石灰（ＣａＯ）を主成分とするものが多く用いられている。この場合、生石灰が硫黄（Ｓ）と反応する脱硫反応が起き、硫黄は硫化カルシウムとなって取り除かれる。この脱硫反応は、塩基度が高いほど進行しやすいことから、蛍石（ＣａＦ２）等の成分が配合される。 Generally, as a desulfurizing agent for steel, a desulfurizing agent containing quicklime (CaO) as a main component is often used. In this case, a desulfurization reaction occurs in which quicklime reacts with sulfur (S), and sulfur is removed as calcium sulfide. Since this desulfurization reaction is more likely to proceed as the basicity is higher, a component such as fluorite (CaF 2 ) is blended.
この種の鉄鋼用の脱硫剤が例えば特許文献１に開示されている。この従来構成の脱硫剤は、転炉滓１０～４０質量％に対し、酸化カルシウム（生石灰）が５５～８５質量％及び蛍石が１０質量％以下配合されている。この脱硫剤によれば、スラグの滓化性が高められ、脱硫率が向上する。 A desulfurizing agent for this type of steel is disclosed in, for example, Patent Document 1. This conventional desulfurization agent contains 55 to 85% by mass of calcium oxide (quick lime) and 10% by mass or less of fluorite with respect to 10 to 40% by mass of the converter slag. According to this desulfurization agent, the slag slagging property is enhanced and the desulfurization rate is improved.
前記特許文献１に記載されている従来構成の脱硫剤には蛍石が含まれていることによって脱硫剤の塩基度が高められ、溶融スラグの流動性が良好になって脱硫反応の促進が図られる。その結果、溶湯の脱硫率が実用上有用な程度まで高められる。しかしながら、蛍石はフッ素化合物であり、フッ素原子を有していることから、脱硫後にはスラグ中にフッ素が残存し、スラグの廃棄時や利用時にスラグからフッ素が溶出し、そのフッ素が環境を汚染するという問題があった。このため、蛍石等のフッ素化合物を使用することなく、フッ素化合物を使用したときと同等の脱硫性能が得られる脱硫剤の代替品が求められている。 Since the desulfurizing agent having the conventional structure described in Patent Document 1 contains fluorite, the basicity of the desulfurizing agent is enhanced, the fluidity of the molten slag is improved, and the desulfurization reaction is promoted. Will be. As a result, the desulfurization rate of the molten metal is increased to a practically useful level. However, since fluorite is a fluorine compound and has a fluorine atom, fluorine remains in the slag after desulfurization, and fluorine elutes from the slag when the slag is discarded or used, and the fluorine affects the environment. There was the problem of contamination. Therefore, there is a demand for a substitute for a desulfurizing agent that can obtain the same desulfurization performance as when a fluorine compound is used without using a fluorine compound such as fluorite.
そこで、この発明の目的とするところは、フッ素化合物を用いることなく、スラグの粘度を下げることができて、脱硫率の向上を図ることができる鉄鋼用脱硫助剤及びその製造方法を提供することにある。 Therefore, an object of the present invention is to provide a desulfurization aid for steel and a method for producing the same, which can reduce the viscosity of slag and improve the desulfurization rate without using a fluorine compound. It is in.
上記の目的を達成するために、この発明の鉄鋼用脱硫助剤は、鉄鋼製錬炉内の溶湯に含まれる硫黄分と反応し、その硫黄分の除去を促進するために酸化カルシウムとともに用いられる鉄鋼用脱硫助剤であって、酸化マグネシウム（ＭｇＯ）及び溶湯の表面に存在するスラグに溶融し、スラグを低粘度化する塩素系化合物を含有することを特徴とする。 In order to achieve the above object, the desulfurization aid for steel of the present invention is used together with calcium oxide to react with sulfur contained in the molten metal in the steel smelting furnace and promote the removal of the sulfur. It is a desulfurization aid for steel, and is characterized by containing magnesium oxide (MgO) and a chlorine-based compound that melts in slag existing on the surface of the molten metal to reduce the viscosity of the slag.
前記塩素系化合物は、塩化水酸化カルシウム〔ＣａＣｌ（ＯＨ）〕又は塩化水酸化マグネシウム〔ＭｇＣｌ（ＯＨ）〕であることが好ましい。
前記酸化マグネシウム１００質量部に対して塩素系化合物の含有量が５～５０質量部であることが好ましい。
The chlorine-based compound is preferably calcium chloride [CaCl (OH)] or magnesium chloride [MgCl (OH)].
The content of the chlorine-based compound is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the magnesium oxide.
二酸化珪素を、酸化マグネシウム１００質量部に対して５～２０質量部含有することが好ましい。
前記鉄鋼用脱硫助剤の製造方法は、酸化マグネシウム及び溶湯の表面に存在するスラグに溶融し、スラグを低粘度化する塩素系化合物を含有する混合物を加圧成形して造粒物を調製することを特徴とする。
It is preferable that silicon dioxide is contained in an amount of 5 to 20 parts by mass with respect to 100 parts by mass of magnesium oxide.
The method for producing a desulfurization aid for steel is to prepare a granule by press-molding a mixture containing magnesium oxide and a chlorine-based compound that melts into slag existing on the surface of the molten metal to reduce the viscosity of the slag. It is characterized by that.
前記鉄鋼用脱硫助剤の製造方法は、マグネシウム源及び塩素源を含有する混合物を造粒して造粒物を成形し、その造粒物を焼成することを特徴とする。
前記マグネシウム源は炭酸マグネシウム、水酸化マグネシウム又はドロマイトであり、塩素源は塩化カルシウム又は塩化マグネシウムであることが好ましい。
The method for producing a desulfurization aid for steel is characterized in that a mixture containing a magnesium source and a chlorine source is granulated to form a granulated product, and the granulated product is calcined.
The magnesium source is preferably magnesium carbonate, magnesium hydroxide or dolomite, and the chlorine source is preferably calcium chloride or magnesium chloride.
前記造粒物を焼成した後、破砕又は粉砕して平均粒子径が１ｍｍ未満の細粒物とすることが好ましい。 It is preferable that the granulated product is fired and then crushed or crushed to obtain fine particles having an average particle size of less than 1 mm.
この発明の鉄鋼用脱硫助剤によれば、フッ素化合物を用いることなく、スラグの粘度を下げることができて、脱硫率の向上を図ることができるという効果を奏する。 According to the desulfurization aid for steel of the present invention, there is an effect that the viscosity of slag can be lowered and the desulfurization rate can be improved without using a fluorine compound.
以下に、この発明を具体化した実施形態について詳細に説明する。
本実施形態における鉄鋼用脱硫助剤（以下、単に脱硫助剤ともいう）は、鉄鋼製錬炉内の溶湯に含まれる硫黄（Ｓ）分と反応し、その硫黄分の除去を促進するために、酸化カルシウム（生石灰、ＣａＯ）に配合され、鉄鋼用脱硫剤として使用されるものである。すなわち、この鉄鋼用脱硫助剤は、酸化カルシウムに蛍石が配合された従来構成の鉄鋼用脱硫剤における蛍石の代替品となるものである。
Hereinafter, embodiments embodying the present invention will be described in detail.
The desulfurization aid for steel in the present embodiment (hereinafter, also simply referred to as a desulfurization aid) reacts with the sulfur (S) contained in the molten metal in the steel smelting furnace to promote the removal of the sulfur content. , Calcium oxide (quicklime, CaO), and is used as a desulfurizing agent for steel. That is, this desulfurization aid for steel is a substitute for fluorite in the conventional desulfurization agent for steel in which fluorite is mixed with calcium oxide.
この鉄鋼用脱硫助剤は、酸化マグネシウム（ＭｇＯ）及び溶湯の表面に存在するスラグ（鉱滓）に溶融し、スラグを低粘度化する塩素系化合物を必須成分として含有する。酸化マグネシウムに塩素系化合物を配合することにより、スラグに対する鉄鋼用脱硫助剤の溶融性を高めることができるとともに、スラグの流動性（粘性）を向上させ、脱硫反応の効率を高めることができる。 This desulfurization aid for steel contains magnesium oxide (MgO) and a chlorine-based compound that melts in slag (mineral slag) existing on the surface of the molten metal to reduce the viscosity of the slag as essential components. By blending a chlorine-based compound with magnesium oxide, the meltability of the desulfurization aid for steel with respect to slag can be enhanced, the fluidity (viscosity) of the slag can be improved, and the efficiency of the desulfurization reaction can be enhanced.
前記酸化マグネシウムは、酸化カルシウムと同様に溶湯中の硫黄と直接反応（脱硫反応）し、溶湯から不純物の硫黄を除去することができる。このとき、酸化マグネシウム及び酸化カルシウムは、溶湯中の燐（Ｐ）分とも同様に反応することから、燐も除去することができる。 Similar to calcium oxide, the magnesium oxide directly reacts with sulfur in the molten metal (desulfurization reaction), and the sulfur impurities can be removed from the molten metal. At this time, since magnesium oxide and calcium oxide react with the phosphorus (P) component in the molten metal in the same manner, phosphorus can also be removed.
前記塩素系化合物は、溶湯に対する酸化マグネシウムや酸化カルシウムの溶融性を高めるとともに、スラグを低粘度化してその流動性（粘性）を向上させ、脱硫反応の効率を高めることができる。この塩素系化合物として具体的には、塩化水酸化カルシウム〔ＣａＣｌ（ＯＨ）〕、塩化水酸化マグネシウム〔ＭｇＣｌ（ＯＨ）〕等が挙げられる。塩化水酸化カルシウムは、スラグに対する酸化マグネシウムや酸化カルシウムの溶融性を高めるとともに、スラグを低粘度化して流動性を改善し、脱硫性能を向上させる。 The chlorine-based compound can increase the meltability of magnesium oxide and calcium oxide in the molten metal, reduce the viscosity of the slag, improve its fluidity (viscosity), and increase the efficiency of the desulfurization reaction. Specific examples of the chlorine-based compound include calcium chloride [CaCl (OH)] and magnesium chloride [MgCl (OH)]. Calcium chloride increases the meltability of magnesium oxide and calcium oxide with respect to slag, and lowers the viscosity of slag to improve fluidity and improve desulfurization performance.
また、塩化水酸化マグネシウムも、スラグ中への酸化マグネシウムや酸化カルシウムの溶融性を高め、スラグの低粘度化により流動性を改善し、脱硫性能を向上させる。このため、塩化水酸化マグネシウムは塩化水酸化カルシウムと相乗的に作用し、脱硫率を向上させることができる。 Further, magnesium hydroxide hydroxide also enhances the meltability of magnesium oxide and calcium oxide in slag, improves the fluidity by lowering the viscosity of the slag, and improves the desulfurization performance. Therefore, magnesium hydroxide can act synergistically with calcium hydroxide to improve the desulfurization rate.
前記鉄鋼用脱硫剤助中の塩素系化合物の配合量は、酸化マグネシウム１００質量部に対して塩素系化合物の含有量が５～５０質量部であることが好ましい。前記塩素系溶融物の含有量が５質量部を下回る場合には、スラグの粘度が高く、流動性の改善が難しくなるとともに、スラグ中での脱硫助剤の溶融速度を高めることも難しくなる。その一方、塩素系化合物の含有量が５０質量部を上回る場合には、スラグが高粘度化したり、酸化マグネシウムの含有量が相対的に減少したりして好ましくない。 The blending amount of the chlorine-based compound in the desulfurizing agent for steel is preferably 5 to 50 parts by mass with respect to 100 parts by mass of magnesium oxide. When the content of the chlorine-based melt is less than 5 parts by mass, the viscosity of the slag is high, it is difficult to improve the fluidity, and it is also difficult to increase the melting rate of the desulfurization aid in the slag. On the other hand, when the content of the chlorine-based compound exceeds 50 parts by mass, the slag becomes highly viscous and the content of magnesium oxide is relatively reduced, which is not preferable.
前記塩素系化合物のうち塩化水酸化カルシウムの含有量は、酸化マグネシウム１００質量部に対して５～４５質量部であることが好ましい。塩化水酸化カルシウムの含有量が５質量部より少ない場合、酸化カルシウムや酸化マグネシウムとの相乗的な機能を十分に発現することが難しくなって好ましくない。その一方、塩化水酸化カルシウムの含有量が４５質量部より多い場合、酸化カルシウムや酸化マグネシウムの含有量が相対的に減少して脱硫助剤の本来の機能を発揮することが困難になる。 The content of calcium chloride in the chlorine-based compound is preferably 5 to 45 parts by mass with respect to 100 parts by mass of magnesium oxide. When the content of calcium hydroxide hydroxide is less than 5 parts by mass, it is difficult to sufficiently exhibit the synergistic function with calcium oxide and magnesium oxide, which is not preferable. On the other hand, when the content of calcium hydroxide hydroxide is more than 45 parts by mass, the content of calcium oxide and magnesium oxide is relatively reduced, and it becomes difficult to exert the original function of the desulfurization aid.
前記塩素系化合物のうち塩化水酸化マグネシウムの含有量は、酸化マグネシウム１００質量部に対して２～１０質量部であることが好ましい。塩化水酸化マグネシウムの含有量が２質量部未満の場合、塩化水酸化マグネシウムの機能発現が不足するとともに、塩化水酸化カルシウムとの相乗作用も得られず好ましくない。一方、塩化水酸化マグネシウムの含有量が１０質量部を超える場合、他の必須成分とのバランスが悪くなるとともに、他成分の含有量が相対的に減少して好ましくない。 The content of magnesium hydroxide chloride among the chlorine-based compounds is preferably 2 to 10 parts by mass with respect to 100 parts by mass of magnesium oxide. When the content of magnesium hydroxide is less than 2 parts by mass, the functional expression of magnesium hydroxide is insufficient and synergistic action with calcium hydroxide cannot be obtained, which is not preferable. On the other hand, when the content of magnesium hydroxide exceeds 10 parts by mass, the balance with other essential components becomes poor and the content of other components is relatively reduced, which is not preferable.
前記鉄鋼用脱硫助剤には、二酸化珪素（シリカ、ＳｉＯ２）を配合することが望ましい。この二酸化珪素を配合することにより、スラグ中における酸化カルシウム、酸化マグネシウム及び塩素系化合物の溶解性を一層高めることができるとともに、スラグの粘度低下を図ることができる。 It is desirable to add silicon dioxide (silica, SiO 2 ) to the desulfurization aid for steel. By blending this silicon dioxide, the solubility of calcium oxide, magnesium oxide and chlorine-based compounds in slag can be further enhanced, and the viscosity of slag can be lowered.
この二酸化珪素の配合量は、酸化マグネシウム１００質量部に対して５～２０質量部であることが好ましい。二酸化珪素の配合量が５質量部より少ない場合、スラグ中における脱硫助剤の各成分の溶解性を高めることが難しく、スラグの低粘度化を図ることが困難である。一方、二酸化珪素の配合量が２０質量部より多い場合、脱硫助剤の他成分の配合量が低下して成分間のバランスが悪くなり、スラグ中への各成分の溶解を妨げ、スラグの低粘度化が難しくなる。 The blending amount of this silicon dioxide is preferably 5 to 20 parts by mass with respect to 100 parts by mass of magnesium oxide. When the blending amount of silicon dioxide is less than 5 parts by mass, it is difficult to increase the solubility of each component of the desulfurization aid in the slag, and it is difficult to reduce the viscosity of the slag. On the other hand, when the blending amount of silicon dioxide is more than 20 parts by mass, the blending amount of other components of the desulfurization aid decreases, the balance between the components becomes poor, the dissolution of each component in the slag is hindered, and the slag is low. Viscosity becomes difficult.
前記鉄鋼用脱硫助剤にはカーボン（Ｃ）、カルシウムアルミネート（ＣａＯ・Ａｌ２Ｏ３）等のその他の添加成分を含有することができる。カーボンを含有することにより、スラグに対する脱硫助剤の溶融速度を高めることができる。また、カルシウムアルミネートは融点が低いことから、スラグに対する脱硫助剤の溶融速度を向上させることができる。 The desulfurization aid for steel can contain other additive components such as carbon (C) and calcium aluminate (CaO · Al 2 O 3 ). By containing carbon, the melting rate of the desulfurization aid for slag can be increased. Further, since calcium aluminate has a low melting point, the melting rate of the desulfurization aid for slag can be improved.
前述のように、鉄鋼用脱硫助剤は酸化カルシウムに配合されて使用される。この場合、鉄鋼用脱硫助剤と酸化カルシウムとの配合量は、鉄鋼用脱硫助剤が１０～５０質量％、酸化カルシウムが５０～９０質量％であることが好ましい。鉄鋼用脱硫助剤が１０質量％未満の場合又は酸化カルシウムが９０質量％を超える場合には、スラグの粘性が高く、流動性が低下して脱硫反応の進行が妨げられるおそれがある。一方、鉄鋼用脱硫助剤が５０質量％を超える場合又は酸化カルシウムが５０質量％未満の場合には、酸化カルシウムと硫黄との脱硫反応や酸化カルシウムと燐との反応が低下する傾向を示して好ましくない。 As described above, the desulfurization aid for steel is used by being mixed with calcium oxide. In this case, the blending amount of the desulfurization aid for steel and calcium oxide is preferably 10 to 50% by mass for the desulfurization aid for steel and 50 to 90% by mass for calcium oxide. When the desulfurization aid for steel is less than 10% by mass or the calcium oxide is more than 90% by mass, the viscosity of the slag is high, the fluidity is lowered, and the progress of the desulfurization reaction may be hindered. On the other hand, when the desulfurization aid for steel exceeds 50% by mass or the calcium oxide is less than 50% by mass, the desulfurization reaction between calcium oxide and sulfur and the reaction between calcium oxide and phosphorus tend to decrease. Not preferred.
本実施形態の鉄鋼用脱硫助剤は、酸化カルシウムとは別体で調整して使用される。そして、鉄鋼用脱硫助剤を鉄鋼用脱硫剤として使用する場合には、鉄鋼用脱硫助剤を酸化カルシウムに添加した混合物として溶湯に投入し、或いは鉄鋼用脱硫助剤と酸化カルシウムをそれぞれ溶湯に投入して使用される。 The desulfurization aid for steel of the present embodiment is prepared and used separately from calcium oxide. When the desulfurization aid for steel is used as the desulfurization agent for steel, the desulfurization aid for steel is added to the molten metal as a mixture of calcium oxide, or the desulfurization aid for steel and calcium oxide are added to the molten metal, respectively. It is thrown in and used.
次に、前述した鉄鋼用脱硫助剤の製造方法について説明する。
この鉄鋼用脱硫助剤の製造方法としては、２つの製造方法が挙げられる。
鉄鋼用脱硫助剤の第１の製造方法は、酸化マグネシウム、塩素系化合物及び所望により二酸化珪素等のその他の添加成分を含有する混合物を加圧成形して造粒物を調製するものである。この製造方法では、必須成分を含有する混合物を加圧成形するだけで鉄鋼用脱硫助剤を簡易に製造することができる。
Next, a method for producing the above-mentioned desulfurization aid for steel will be described.
As a method for producing this desulfurization aid for steel, there are two production methods.
The first method for producing a desulfurization aid for steel is to prepare a granulated product by pressure-molding a mixture containing magnesium oxide, a chlorine-based compound and, if desired, other additive components such as silicon dioxide. In this production method, a desulfurization aid for steel can be easily produced only by pressure forming a mixture containing essential components.
この場合、前記混合物中の各成分の配合量は、鉄鋼用脱硫助剤における各成分の含有量が適用される。加圧成形（プレス成形）は常法に従って行われ、得られる造粒物の平均粒子径は、例えば５～４０ｍｍである。 In this case, the content of each component in the desulfurization aid for steel is applied to the blending amount of each component in the mixture. Pressure molding (press molding) is performed according to a conventional method, and the average particle size of the obtained granulated product is, for example, 5 to 40 mm.
鉄鋼用脱硫助剤の第２の製造方法は、マグネシウム源、塩素源及び所望により二酸化珪素等のその他の添加成分を含有する混合物を加圧成形（プレス成形）して造粒物を成形し、その造粒物を焼成するものである。加圧成形は常法に従って行われ、得られる造粒物の平均粒子径は例えば５～４０ｍｍである。 The second method for producing a desulfurization aid for steel is to press-mold (press-mold) a mixture containing a magnesium source, a chlorine source and, if desired, other additive components such as silicon dioxide to form granules. The granulated product is fired. The pressure molding is performed according to a conventional method, and the average particle size of the obtained granulated product is, for example, 5 to 40 mm.
前記マグネシウム源としては酸化マグネシウム、炭酸マグネシウム、水酸化マグネシウム、マグネサイト又はドロマイト及び塩素源としては塩化カルシウム又は塩化マグネシウムが好ましい。焼成温度は９００～１２００℃の範囲が好ましく、９５０～１１００℃の範囲がより好ましい。 The magnesium source is preferably magnesium oxide, magnesium carbonate, magnesium hydroxide, magnetite or dolomite, and the chlorine source is preferably calcium chloride or magnesium chloride. The firing temperature is preferably in the range of 900 to 1200 ° C, more preferably in the range of 950 to 1100 ° C.
焼成温度が９００℃未満ではマグネシウム源から酸化マグネシウムを生成することが難しく、１２００℃を超えると塩素揮発量が増大して塩化水酸化マグネシウムの生成量が低下して好ましくない。この製造方法では、焼成後に必須成分として酸化マグネシウム及び塩素系化合物が生成する。 If the firing temperature is less than 900 ° C, it is difficult to produce magnesium oxide from the magnesium source, and if it exceeds 1200 ° C, the amount of chlorine volatilized increases and the amount of magnesium hydroxide produced decreases, which is not preferable. In this production method, magnesium oxide and a chlorine-based compound are produced as essential components after firing.
前記造粒物を焼成した後には、破砕又は粉砕して細粒物を形成することが好ましい。このようにして得られる鉄鋼用脱硫助剤の細粒物は、スラグに対する鉄鋼用脱硫助剤の溶融を促し、スラグの流動性を改善し、脱硫率を高めることができる。該細粒物の平均粒子径は１ｍｍ未満であることが望ましい。なお、この細粒物の平均粒子径の下限は、１μｍ程度である。 After firing the granulated product, it is preferable to crush or pulverize the granulated product to form fine granules. The fine granules of the desulfurization aid for steel obtained in this manner can promote the melting of the desulfurization aid for steel with respect to the slag, improve the fluidity of the slag, and increase the desulfurization rate. The average particle size of the fine particles is preferably less than 1 mm. The lower limit of the average particle size of the fine particles is about 1 μm.
次に、前記のように構成された鉄鋼用脱硫助剤について作用を説明する。
さて、鉄鋼製錬炉内の溶湯に含まれる硫黄分等の不純物を取り除く場合には、溶湯に対して所定量の鉄鋼用脱硫助剤を酸化カルシウムとともに添加して撹拌する。このとき、鉄鋼用脱硫助剤中には必須成分として酸化マグネシウム及びスラグに溶融し、スラグを低粘度化する塩素系化合物が含まれている。
Next, the action of the desulfurization aid for steel configured as described above will be described.
When removing impurities such as sulfur contained in the molten metal in the steel smelting furnace, a predetermined amount of desulfurization aid for steel is added to the molten metal together with calcium oxide and stirred. At this time, the desulfurization aid for steel contains magnesium oxide and a chlorine-based compound that melts into slag to reduce the viscosity of the slag as essential components.
このため、酸化マグネシウムが酸化カルシウムとともに溶湯とスラグとの界面で硫黄と反応する脱硫反応が起き、硫黄は硫化マグネシウムや硫化カルシウムとなって取り除かれる。このとき、鉄鋼用脱硫助剤には塩素系化合物としての塩化水酸化カルシウム、塩化水酸化マグネシウムが含まれていることから、スラグに対して酸化マグネシウムや酸化カルシウムが速やかに溶融し、酸化マグネシウム及び酸化カルシウムの機能が迅速かつ有効に発現される。 Therefore, a desulfurization reaction occurs in which magnesium oxide reacts with calcium at the interface between the molten metal and slag together with calcium oxide, and sulfur is removed as magnesium sulfide or calcium sulfide. At this time, since the desulfurization aid for steel contains calcium chloride and magnesium chloride as chlorine-based compounds, magnesium oxide and calcium oxide are rapidly melted with respect to the slag, and magnesium oxide and magnesium oxide and magnesium oxide are rapidly melted. The function of calcium oxide is rapidly and effectively expressed.
加えて、塩素系化合物としての塩化水酸化カルシウム、塩化水酸化マグネシウムはスラグを低粘度化してその流動性を改善することができる。その結果、鉄鋼用脱硫助剤の脱硫性能は一層向上し、脱硫反応が促進されて脱硫率の向上が図られる。 In addition, calcium chloride and magnesium hydroxide as chlorine compounds can reduce the viscosity of slag and improve its fluidity. As a result, the desulfurization performance of the desulfurization aid for steel is further improved, the desulfurization reaction is promoted, and the desulfurization rate is improved.
従って、この実施形態によれば、以下のような効果を得ることができる。
（１）この実施形態の鉄鋼用脱硫助剤は、必須成分として酸化マグネシウム及び塩素系化合物を含有する。塩素系化合物は、スラグに溶融するとともに、スラグを低粘度化し、脱硫反応を促すことができる。
Therefore, according to this embodiment, the following effects can be obtained.
(1) The desulfurization aid for steel of this embodiment contains magnesium oxide and a chlorine-based compound as essential components. The chlorine-based compound melts into slag, lowers the viscosity of the slag, and promotes a desulfurization reaction.
従って、実施形態の鉄鋼用脱硫助剤によれば、フッ素化合物を用いることなく、スラグの粘度を下げることができて、脱硫率の向上を図ることができる。加えて、この鉄鋼用脱硫助剤はフッ素化合物を含まないように構成することができ、脱硫後のスラグからフッ素を溶出するおそれがなく、環境汚染を回避することができる。 Therefore, according to the desulfurization aid for steel of the embodiment, the viscosity of the slag can be lowered and the desulfurization rate can be improved without using a fluorine compound. In addition, this desulfurization aid for steel can be configured so as not to contain a fluorine compound, there is no possibility of elution of fluorine from the slag after desulfurization, and environmental pollution can be avoided.
（２）前記塩素系化合物は、塩化水酸化カルシウム又は塩化水酸化マグネシウムである。この場合、鉄鋼用脱硫助剤は、スラグの低粘度化を促してスラグの流動性を良好にでき、脱硫反応を促進することができる。 (2) The chlorine-based compound is calcium chloride hydroxide or magnesium hydroxide. In this case, the desulfurization aid for steel can promote the low viscosity of the slag, improve the fluidity of the slag, and promote the desulfurization reaction.
（３）前記酸化マグネシウム１００質量部に対して塩素系化合物の含有量は５～５０質量部である。このため、各必須成分の機能をバランス良く発揮することができ、脱硫率を高めることができる。 (3) The content of the chlorine-based compound is 5 to 50 parts by mass with respect to 100 parts by mass of the magnesium oxide. Therefore, the functions of each essential component can be exhibited in a well-balanced manner, and the desulfurization rate can be increased.
（４）前記鉄鋼用脱硫助剤には、二酸化珪素が酸化マグネシウム１００質量部に対して５～２０質量部含まれる。この場合には、スラグ中における酸化カルシウム、酸化マグネシウム及び塩素系化合物の溶融性を一層高めることができるとともに、スラグの粘度低下を図ることができる。 (4) The desulfurization aid for steel contains 5 to 20 parts by mass of silicon dioxide with respect to 100 parts by mass of magnesium oxide. In this case, the meltability of calcium oxide, magnesium oxide and the chlorine-based compound in the slag can be further enhanced, and the viscosity of the slag can be lowered.
（５）鉄鋼用脱硫助剤の第１の製造方法は、酸化マグネシウム及び塩素系化合物を含有する混合物を加圧成形して造粒物を調製する。この製造方法によれば、焼成を行うことなく、加圧成形のみにより鉄鋼用脱硫助剤を簡易に製造することができる。 (5) The first method for producing a desulfurization aid for steel is to prepare a granulated product by pressure molding a mixture containing magnesium oxide and a chlorine-based compound. According to this manufacturing method, a desulfurization aid for steel can be easily manufactured only by pressure forming without firing.
（６）鉄鋼用脱硫助剤の第２の製造方法は、マグネシウム源及び塩素源を含有する混合物を造粒して造粒物を成形し、その造粒物を焼成するものである。この製造方法によれば、焼成により鉄鋼用脱硫助剤の必須成分を生成させることができ、その必須成分を含む造粒物を得ることができる。 (6) The second method for producing a desulfurization aid for steel is to granulate a mixture containing a magnesium source and a chlorine source to form a granulated product, and then calcin the granulated product. According to this production method, an essential component of a desulfurization aid for steel can be produced by firing, and a granulated product containing the essential component can be obtained.
（７）前記マグネシウム源は炭酸マグネシウム、水酸化マグネシウム又はドロマイトであり、塩素源は塩化カルシウム又は塩化マグネシウムである。この場合、焼成後に鉄鋼用脱硫助剤中における必須成分の生成率を高めることができる。 (7) The magnesium source is magnesium carbonate, magnesium hydroxide or dolomite, and the chlorine source is calcium chloride or magnesium chloride. In this case, it is possible to increase the production rate of essential components in the desulfurization aid for steel after firing.
（８）前記造粒物を焼成した後、破砕又は粉砕して平均粒子径が１ｍｍ未満の細粒物とする。この場合には、鉄鋼用脱硫助剤の細粒物により、脱硫性能の向上を図ることができる。 (8) After firing the granulated product, it is crushed or crushed to obtain fine particles having an average particle size of less than 1 mm. In this case, the desulfurization performance can be improved by using fine particles of the desulfurization aid for steel.
以下、実施例、比較例及び対照例を挙げて前記実施形態をさらに具体的に説明する。なお、以下の各例において、部は質量部を表す。表１～表３中の数値も質量部を表す。
（実施例１）
炭酸マグネシウム８０部に対して塩化カルシウム２０部を混合し、常法によりプレス成形して造粒物を得た。この造粒物を１０５０℃で焼成して、平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示した。また、鉄鋼用脱硫助剤の組成をＸ線回折及び蛍光Ｘ線分析によって分析し、その結果を表３に示した。
Hereinafter, the embodiment will be described in more detail with reference to Examples, Comparative Examples, and Control Examples. In each of the following examples, the part represents a mass part. The numerical values in Tables 1 to 3 also represent parts by mass.
(Example 1)
20 parts of calcium chloride was mixed with 80 parts of magnesium carbonate and press-molded by a conventional method to obtain granulated products. This granulated product was calcined at 1050 ° C. to prepare a desulfurization aid for steel as a granulated product having an average particle size of 5 to 40 mm. The raw material composition of this desulfurization aid for steel is shown in Table 1. The composition of the desulfurization aid for steel was analyzed by X-ray diffraction and fluorescent X-ray analysis, and the results are shown in Table 3.
（実施例２）
炭酸マグネシウム９０部に対して塩化カルシウム１０部を混合し、常法によりプレス成形して造粒物を得た。この造粒物を１０５０℃で焼成して、平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示した。また、鉄鋼用脱硫助剤の組成をＸ線回折及び蛍光Ｘ線分析によって分析し、その結果を表３に示した。
(Example 2)
10 parts of calcium chloride was mixed with 90 parts of magnesium carbonate and press-molded by a conventional method to obtain granulated products. This granulated product was calcined at 1050 ° C. to prepare a desulfurization aid for steel as a granulated product having an average particle size of 5 to 40 mm. The raw material composition of this desulfurization aid for steel is shown in Table 1. The composition of the desulfurization aid for steel was analyzed by X-ray diffraction and fluorescent X-ray analysis, and the results are shown in Table 3.
（実施例３）
実施例１で得られた鉄鋼用脱硫助剤を粉砕し、細粒化して平均粒子径が１ｍｍ未満（１μｍ以上）となる細粒物として実施例３の鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示し、Ｘ線回折及び蛍光Ｘ線分析により分析した鉄鋼用脱硫助剤の組成を表３に示した。
(Example 3)
The desulfurization aid for steel obtained in Example 1 was pulverized and granulated to prepare a desulfurization aid for steel of Example 3 as fine particles having an average particle size of less than 1 mm (1 μm or more). The raw material composition of this desulfurization aid for steel is shown in Table 1, and the composition of the desulfurization aid for steel analyzed by X-ray diffraction and fluorescent X-ray analysis is shown in Table 3.
（実施例４）
酸化マグネシウム６５部に対して、塩化水酸化カルシウム２５部及び塩化水酸化マグネシウム１０部を混合し、常法によりプレス成形した後、粉砕して平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の組成を表１に示した。
(Example 4)
25 parts of calcium hydroxide and 10 parts of magnesium hydroxide are mixed with 65 parts of magnesium oxide, press-molded by a conventional method, and then pulverized to form a granulated product having an average particle size of 5 to 40 mm for steel. A desulfurization aid was prepared. The composition of this desulfurization aid for steel is shown in Table 1.
（実施例５）
炭酸マグネシウム８２部に対して塩化カルシウム１６部及び二酸化珪素２部を混合し、常法によりプレス成形して造粒物を得た。この造粒物を１０５０℃で焼成して、平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示した。また、鉄鋼用脱硫助剤の組成をＸ線回折及び蛍光Ｘ線分析によって分析し、その結果を表３に示した。
(Example 5)
16 parts of calcium chloride and 2 parts of silicon dioxide were mixed with 82 parts of magnesium carbonate and press-molded by a conventional method to obtain granulated products. This granulated product was calcined at 1050 ° C. to prepare a desulfurization aid for steel as a granulated product having an average particle size of 5 to 40 mm. The raw material composition of this desulfurization aid for steel is shown in Table 1. The composition of the desulfurization aid for steel was analyzed by X-ray diffraction and fluorescent X-ray analysis, and the results are shown in Table 3.
（実施例６）
炭酸マグネシウム８２部に対して塩化カルシウム１２部及び二酸化珪素６部を混合し、常法によりプレス成形して造粒物を得た。この造粒物を１０５０℃で焼成して、平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示した。また、鉄鋼用脱硫助剤の組成をＸ線回折及び蛍光Ｘ線分析によって分析し、その結果を表３に示した。
(Example 6)
12 parts of calcium chloride and 6 parts of silicon dioxide were mixed with 82 parts of magnesium carbonate and press-molded by a conventional method to obtain granulated products. This granulated product was calcined at 1050 ° C. to prepare a desulfurization aid for steel as a granulated product having an average particle size of 5 to 40 mm. The raw material composition of this desulfurization aid for steel is shown in Table 1. The composition of the desulfurization aid for steel was analyzed by X-ray diffraction and fluorescent X-ray analysis, and the results are shown in Table 3.
（実施例７）
炭酸マグネシウム８１部に対して塩化カルシウム１１部及び二酸化珪素８部を混合し、常法によりプレス成形して造粒物を得た。この造粒物を１０５０℃で焼成して、平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の原料組成を表１に示した。また、鉄鋼用脱硫助剤の組成をＸ線回折及び蛍光Ｘ線分析によって分析し、その結果を表３に示した。
(Example 7)
11 parts of calcium chloride and 8 parts of silicon dioxide were mixed with 81 parts of magnesium carbonate and press-molded by a conventional method to obtain granulated products. This granulated product was calcined at 1050 ° C. to prepare a desulfurization aid for steel as a granulated product having an average particle size of 5 to 40 mm. The raw material composition of this desulfurization aid for steel is shown in Table 1. The composition of the desulfurization aid for steel was analyzed by X-ray diffraction and fluorescent X-ray analysis, and the results are shown in Table 3.
（実施例８）
酸化マグネシウム６５部に対して、塩化水酸化カルシウム２５部、塩化水酸化マグネシウム５部及び二酸化珪素１０部を混合し、常法によりプレス成形した後、粗砕して平均粒子径が５～４０ｍｍの造粒物として鉄鋼用脱硫助剤を調製した。この鉄鋼用脱硫助剤の組成を表１に示した。
(Example 8)
25 parts of calcium hydroxide, 5 parts of magnesium hydroxide and 10 parts of silicon dioxide are mixed with 65 parts of magnesium oxide, press-molded by a conventional method, and then coarsely crushed to have an average particle size of 5 to 40 mm. A desulfurization aid for steel was prepared as a granulated product. The composition of this desulfurization aid for steel is shown in Table 1.
（比較例１）
酸化マグネシウム単体を常法によりプレス成形して造粒物を調整し、比較例１の鉄鋼用脱硫剤とした。この鉄鋼用脱硫剤の組成を表２に示した。
(Comparative Example 1)
A simple substance of magnesium oxide was press-molded by a conventional method to prepare a granulated product, which was used as a desulfurizing agent for steel in Comparative Example 1. The composition of this desulfurizing agent for steel is shown in Table 2.
（比較例２）
酸化カルシウム単体を常法によりプレス成形して造粒物を調整し、比較例２の鉄鋼用脱硫剤とした。この鉄鋼用脱硫剤の組成を表２に示した。
(Comparative Example 2)
A simple substance of calcium oxide was press-molded by a conventional method to prepare a granulated product, which was used as a desulfurizing agent for steel in Comparative Example 2. The composition of this desulfurizing agent for steel is shown in Table 2.
（比較例３）
塩化カルシウム単体を常法によりプレス成形して造粒物を調整し、比較例３の鉄鋼用脱硫剤とした。この鉄鋼用脱硫剤の組成を表２に示した。
(Comparative Example 3)
A simple substance of calcium chloride was press-molded by a conventional method to prepare a granulated product, which was used as a desulfurizing agent for steel in Comparative Example 3. The composition of this desulfurizing agent for steel is shown in Table 2.
（対照例１）
酸化カルシウム６７部に対してフッ化カルシウム粉を３３部混合し、常法によりプレス成形して対照例１の鉄鋼用脱硫剤を調製した。
(Control Example 1)
33 parts of calcium fluoride powder was mixed with 67 parts of calcium oxide and press-molded by a conventional method to prepare a desulfurizing agent for steel of Control Example 1.
前記加熱によりスラグ成分と鉄鋼用脱硫剤とが溶融して液状になった後、粘度測定用のロッド（ルテニウム２０質量％を含む白金製）を挿入して高温スラグの粘度（ｍＰａ・ｓ）を測定した。その結果を表４に示した。 After the slug component and the desulfurizing agent for steel are melted and liquefied by the heating, a rod for measuring viscosity (made of platinum containing 20% by mass of ruthenium) is inserted to determine the viscosity (mPa · s) of the high temperature slug. It was measured. The results are shown in Table 4.
次に、前記実施例１～８、比較例１～３及び対照例１の鉄鋼用脱硫剤について、高周波誘導炉を使用して脱硫率（％）を測定した。
すなわち、高周波誘導炉内に鉄源５０ｋｇと、硫黄含有率が０．０５質量％となるように硫化鉄とを混合して溶解させ、溶湯を得た。この溶湯に前記鉄鋼用脱硫剤１ｋｇとスラグ成分とを投入し、１５分間撹拌した。その後に溶湯の一部を採取し、硫黄含有率を分析した。そして、下記の計算式に基づいて脱硫率（％）を算出した。その結果を表５に示した。
Next, the desulfurization rate (%) of the steel desulfurization agents of Examples 1 to 8, Comparative Examples 1 to 3 and Control Example 1 was measured using a high-frequency induction furnace.
That is, 50 kg of an iron source and iron sulfide were mixed and dissolved in a high-frequency induction furnace so that the sulfur content was 0.05% by mass to obtain a molten metal. 1 kg of the desulfurizing agent for steel and a slag component were added to this molten metal, and the mixture was stirred for 15 minutes. After that, a part of the molten metal was collected and the sulfur content was analyzed. Then, the desulfurization rate (%) was calculated based on the following formula. The results are shown in Table 5.
脱硫率（％）＝〔（試験前の硫黄含有率－試験後の硫黄含有率）／試験前の硫黄含有率〕×１００ Desulfurization rate (%) = [(Sulfur content before test-Sulfur content after test) / Sulfur content before test] x 100
次に、前記実施例１～８、比較例１～３及び対照例１の鉄鋼用脱硫剤について脱硫速度を測定した。
すなわち、前記脱硫率（％）の測定において、溶湯に鉄鋼用脱硫剤を投入し、その５分後、１０分後及び１５分後における硫黄含有率を測定し、前記計算式に基づいて脱硫率（％）を算出した。その結果を表６に示した。
Next, the desulfurization rates of the steel desulfurization agents of Examples 1 to 8, Comparative Examples 1 to 3 and Control Example 1 were measured.
That is, in the measurement of the desulfurization rate (%), the desulfurization agent for steel was added to the molten metal, the sulfur content was measured 5 minutes, 10 minutes and 15 minutes after that, and the desulfurization rate was measured based on the above formula. (%) Was calculated. The results are shown in Table 6.
（実施例９）
前記実施例１の鉄鋼用脱硫助剤について、焼成温度を１０５０℃、１１００℃、１２００℃及び１３００℃に変化させたときの脱硫率（％）を前述した方法で測定した。そして、焼成温度（℃）と脱硫率（％）との関係を図１に示した。
(Example 9)
For the desulfurization aid for steel of Example 1, the desulfurization rate (%) when the firing temperature was changed to 1050 ° C, 1100 ° C, 1200 ° C and 1300 ° C was measured by the above-mentioned method. The relationship between the firing temperature (° C.) and the desulfurization rate (%) is shown in FIG.
図１に示したように、焼成温度が１１００℃を超えると脱硫率が次第に低下し始める傾向が示された。
さらに、実施例１の鉄鋼用脱硫助剤について、焼成温度９５０℃、１０５０℃、１１５０℃、１４５０℃と、各焼成温度における焼成後の鉄鋼用脱硫剤中の塩素（Ｃｌ）含有率（質量％）を測定することにより、各焼成温度における塩素揮発量（質量％）を算出した。そして、焼成温度（℃）と塩素揮発量（質量％）との関係を図２に示した。
As shown in FIG. 1, when the firing temperature exceeds 1100 ° C., the desulfurization rate tends to gradually decrease.
Further, regarding the desulfurization aid for steel of Example 1, the calcination temperature was 950 ° C., 1050 ° C., 1150 ° C., and 1450 ° C., and the chlorine (Cl) content (mass%) in the calcination agent for steel after calcination at each firing temperature. ) Was measured to calculate the amount of chlorine volatilization (mass%) at each firing temperature. Then, the relationship between the firing temperature (° C.) and the amount of chlorine volatilization (mass%) is shown in FIG.
図２に示したように、焼成温度が１１００℃を超えると塩素揮発量が増大する傾向が見られた。これは、塩化水酸化カルシウムが分解して塩素が揮発しているものと考えられることから、有効成分である塩化水酸化カルシウムを含有させるためには、焼成温度は１１００℃以下であることが望ましい。また、炭酸カルシウムが酸化カルシウムに化学変化するための温度は９５０℃以上であることが好ましい。従って、焼成温度は９５０～１１００℃の範囲であることが好ましい。 As shown in FIG. 2, when the firing temperature exceeds 1100 ° C., the amount of chlorine volatilized tends to increase. It is considered that this is because calcium chloride is decomposed and chlorine is volatilized. Therefore, in order to contain calcium chloride which is an active ingredient, it is desirable that the firing temperature is 1100 ° C. or lower. .. Further, the temperature for chemically changing calcium carbonate to calcium oxide is preferably 950 ° C. or higher. Therefore, the firing temperature is preferably in the range of 950 to 1100 ° C.
なお、前記実施形態は、次のように変更して具体化することも可能である。
・前記鉄鋼用脱硫助剤の必須成分の含有量を、溶湯中の硫黄成分との反応に加えて燐成分との反応をも考慮して総合的に設定してもよい。
The embodiment can be modified and embodied as follows.
-The content of the essential component of the desulfurization aid for steel may be comprehensively set in consideration of the reaction with the phosphorus component in addition to the reaction with the sulfur component in the molten metal.
・前記鉄鋼用脱硫助剤の第１の製造方法において、塩化水酸化カルシウムと塩化水酸化マグネシウムのいずれか一方のみを使用してもよい。
・前記鉄鋼用脱硫助剤の第２の製造方法において、マグネシウム源又は塩素源は、前記製造方法に示された単一物質に限定されるものではなく、マグネシウム又は塩素を含む物質を複数混合して製造してもよい。
-In the first method for producing the desulfurization aid for steel, only one of calcium chloride and magnesium hydroxide may be used.
-In the second method for producing a desulfurization aid for steel, the magnesium source or chlorine source is not limited to the single substance shown in the production method, and a plurality of substances containing magnesium or chlorine are mixed. May be manufactured.
Claims (8)
酸化マグネシウム及び溶湯の表面に存在するスラグに溶融し、スラグを低粘度化する塩素系化合物を含有することを特徴とする鉄鋼用脱硫助剤。 A desulfurization aid for steel used together with calcium oxide to react with sulfur contained in the molten metal in a steel smelting furnace and promote the removal of the sulfur.
A desulfurization aid for steel, which contains magnesium oxide and a chlorine-based compound that melts into slag existing on the surface of the molten metal to reduce the viscosity of the slag.
酸化マグネシウム及び溶湯の表面に存在するスラグに溶融し、スラグを低粘度化する塩素系化合物を含有する混合物を加圧成形して造粒物を調製することを特徴とする鉄鋼用脱硫助剤の製造方法。 The method for producing a desulfurization aid for steel according to any one of claims 1 to 4.
A desulfurization aid for steel, which is characterized in that a mixture containing magnesium oxide and a chlorine-based compound that melts into slag existing on the surface of molten metal to reduce the viscosity of the slag is pressure-molded to prepare a granulated product. Production method.
マグネシウム源及び塩素源を含有する混合物を造粒して造粒物を成形し、その造粒物を焼成することを特徴とする鉄鋼用脱硫助剤の製造方法。 The method for producing a desulfurization aid for steel according to any one of claims 1 to 4.
A method for producing a desulfurization aid for steel, which comprises granulating a mixture containing a magnesium source and a chlorine source to form a granulated product, and firing the granulated product.
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