JP2012158495A - Furnace wall protection material for steelmaking and method for manufacturing the same - Google Patents
Furnace wall protection material for steelmaking and method for manufacturing the same Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000009628 steelmaking Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 238000010304 firing Methods 0.000 claims abstract description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 154
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 130
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 108
- 239000000292 calcium oxide Substances 0.000 claims description 83
- 235000012255 calcium oxide Nutrition 0.000 claims description 83
- 239000000395 magnesium oxide Substances 0.000 claims description 70
- 230000001681 protective effect Effects 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010459 dolomite Substances 0.000 abstract description 34
- 229910000514 dolomite Inorganic materials 0.000 abstract description 34
- 230000006866 deterioration Effects 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004484 Briquette Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000001095 magnesium carbonate Substances 0.000 description 9
- 235000014380 magnesium carbonate Nutrition 0.000 description 9
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 9
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 9
- 235000019738 Limestone Nutrition 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052599 brucite Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
この発明は、製鋼用炉壁保護材及びその製造方法に関するものである。とくに、この発明は、転炉により鋼を製造する際に用いられる炉壁保護材に関するものであり、またその製造方法に関するものである。 The present invention relates to a furnace wall protective material for steel making and a method for producing the same. In particular, the present invention relates to a furnace wall protective material used when manufacturing steel by a converter and also relates to a manufacturing method thereof.
製鋼用炉壁保護材については、その詳細を記載した文献が少ない。鉄鋼便覧は、転炉により鋼を製造する際に耐火煉瓦からなる炉壁を保護するための炉壁保護材として、生ドロマイト又は軽焼ドロマイトを使用すると記載している。生ドロマイトとしてはＭｇＯが２０重量％以上のものが用いられ、軽焼ドロマイトとしてはＭｇＯが３０重量％以上のものが用いられている。 There are few documents describing the details of the furnace wall protective material for steel making. The steel manual describes that raw dolomite or light-burned dolomite is used as a furnace wall protective material for protecting a furnace wall made of refractory bricks when steel is produced by a converter. As raw dolomite, MgO containing 20% by weight or more is used, and as light-burning dolomite, MgO containing 30% by weight or more is used.
また、杉田清著の「製銑・製鋼用耐火物」は、生ドロマイト又は軽焼ドロマイトを造滓材として使用して転炉内張材を保護する技術が開発され、日本で実用されていると記載している。これは、生ドロマイト又は軽焼ドロマイトが、炉壁保護材として働くことを教えたものである。 Sugita Kiyoshi's “Refractory for Steelmaking and Steelmaking” has been developed and used in Japan to protect converter lining materials using raw dolomite or light-fired dolomite as a steelmaking material. It is described. This teaches that raw dolomite or light-burned dolomite works as a furnace wall protective material.
また、特開２０１０−１３８４２８号公報は、転炉により鋼を作る場合には、発生するスラグにより耐火物が浸食されるので、これを防止して転炉の寿命を延長するために、ＭｇＯを含有するドロマイト又は軽焼ドロマイト、又は転炉解体時に発生するＭｇＯレンガ屑を２０ｍｍ以下に破砕したものを用いることを提案している。 JP 2010-138428 A discloses that when steel is produced by a converter, refractories are eroded by the generated slag, so in order to prevent this and extend the life of the converter, MgO is used. It is proposed to use dolomite or light-burning dolomite contained, or MgO brick scraps generated during dismantling of the converter to be crushed to 20 mm or less.
ドロマイトは、上記文献が記載しているように、炉壁耐火物を保護する物として、有効な成分だとされている。とくに、生ドロマイトは、劣化の原因となるフリーライム（ＣａＯ）が少ない為、或る程度の期間保管をしても劣化、粉化することはほとんどない。ところが、生ドロマイトは加工した製品よりも炉内で溶けにくく、また、ドロマイト鉱石は分解反応時に吸熱して炉湯温度を低下させる。また、ドロマイト鉱石はＣａＯの値が高い為、造滓材として投入する生石灰と合わせると、ＣａＯを過剰に投入することとなり、ＭｇＯの値の調整の為に、使用原単位が増加する。また、ドロマイトには、結合水（Ｈ2Ｏ）が多く含有されているため、鋼に対して害物として働く水素が熔湯内に多く含まれることになり、その結果鋼が脆弱となり易い。 Dolomite is said to be an effective component as a material that protects the furnace wall refractory, as described in the above document. In particular, raw dolomite has little free lime (CaO) that causes deterioration, so it hardly deteriorates or powders even when stored for a certain period of time. However, raw dolomite is less soluble in the furnace than the processed product, and dolomite ore absorbs heat during the decomposition reaction and lowers the furnace water temperature. In addition, since dolomite ore has a high value of CaO, when combined with quicklime added as a kneading material, CaO is excessively added, and the basic unit of use increases for adjusting the value of MgO. Further, since dolomite contains a large amount of bound water (H 2 O), a large amount of hydrogen acting as a harmful substance to the steel is contained in the molten metal, and as a result, the steel tends to be brittle.
上記公報がドロマイトと並べて記載する軽焼ドロマイトは、上記生ドロマイトを焼成したものである。ドロマイトは、理想化学組成がＣａＣＯ3・ＭｇＣＯ3とされるものであるが、軽焼ドロマイトは、ＣａＯ・ＭｇＯの理想化学組成を持つものとされる。その中のＭｇＯは、大気中に放置した場合、ＣａＯほど反応性は強くないが、ＣａＯは吸水してＣａ(ＯＨ)2となり易く、吸水すると体積が増大する。そのため軽焼ドロマイトは製造後、ある程度の期間が経過すると粉化する。従って、軽焼ドロマイトは使用期限が限定される。 The light-burned dolomite described in the above publication alongside dolomite is obtained by firing the raw dolomite. Dolomite has an ideal chemical composition of CaCO 3 · MgCO 3 , while lightly burned dolomite has an ideal chemical composition of CaO · MgO. MgO therein is not as reactive as CaO when left in the atmosphere, but CaO absorbs water easily to become Ca (OH) 2 , and its volume increases when absorbed. For this reason, light-burned dolomite powders after a certain period of time after production. Therefore, the expiration date for light-burned dolomite is limited.
生ドロマイト及び軽焼ドロマイトが持つ上記欠点を改良するものとして、ＭｇＯボールと呼ばれる炉壁保護材が提供されている。ＭｇＯボールは、軽焼ドロマイトの粉末に、結合剤と水とを加えてブリケットにしたものである。この為、ＭｇＯボールは大きさが揃っていて粉末がなく集塵ロスが少ない。また、ＭｇＯボールは、粉末を固めたものである為、溶鋼中に溶解し易く、その上に結合剤で固められているから、ＣａＯの吸湿性が抑えられ、従って使用期間が軽焼ドロマイトよりも長くなっている。また、ＭｇＯ値も高い為、使用原単位の減少となる。この為、ＭｇＯボールは現在も広く使われている。しかし、ＭｇＯボールはなおＣａＯを含むために、３ヶ月程度保管されると、吸水により劣化し、粉化するという欠点をまだ伴なっている。従って、矢張り可使期間が限定されるという欠点を持っている。 A furnace wall protective material called MgO ball has been provided as an improvement on the above-mentioned drawbacks of raw dolomite and light-burned dolomite. The MgO balls are briquettes obtained by adding a binder and water to lightly burned dolomite powder. For this reason, the MgO balls have the same size, no powder, and little dust collection loss. Also, since MgO balls are hardened powder, they are easy to dissolve in molten steel, and since they are hardened with a binder on them, the hygroscopicity of CaO is suppressed, so the service period is shorter than that of light-burned dolomite. Is also getting longer. Also, since the MgO value is high, the basic unit used is reduced. For this reason, MgO balls are still widely used today. However, since the MgO balls still contain CaO, they are still accompanied by the disadvantage that when stored for about 3 months, they deteriorate due to water absorption and powder. Therefore, there is a drawback that the period for which the arrow can be used is limited.
生ドロマイト、軽焼ドロマイト、及びＭｇＯボールのようなマグネシウム含有の添加物は、転炉による製鋼時に転炉の内壁を保護するものとして、絶対必要なものとされている。ところが、これらの添加物はそれぞれ上述のような欠点を持っている。そのため、そのような欠点のない添加物の出現が強く要望されている。 Magnesium-containing additives such as raw dolomite, light-burned dolomite, and MgO balls are considered to be absolutely necessary for protecting the inner wall of the converter during steelmaking by the converter. However, each of these additives has the drawbacks described above. Therefore, there is a strong demand for the appearance of additives that do not have such drawbacks.
この発明は、マグネシウム含有の炉壁保護材についての上記要望を満たそうとしてなされたものである。すなわち、この発明は、ＭｇＯボールの持つ長所をそのまま保有しながら、製造後より長い期間大気中に放置しても粉化することなく、従って製造後可使期間の長い炉壁保護材を提供しようとしてなされたものである。 The present invention has been made to satisfy the above-mentioned demand for a magnesium-containing furnace wall protective material. That is, the present invention aims to provide a furnace wall protective material that retains the advantages of the MgO ball as it is and does not pulverize even if left in the atmosphere for a longer period after manufacture, and therefore has a longer usable period after manufacture. It was made as.
この発明者は、重量で７０部の酸化マグネシウムＭｇＯと、２５部の酸化カルシウムＣａＯと、５部の酸化鉄ＦｅＯを混合して混合物を作り、この混合物を粉砕し、得られた粉末を１４００℃の温度に加熱して焼成し焼結体を作った。そして、この焼結体を大気中に放置して重量の変化などを観察した。その結果、この焼結体は６ヶ月放置しても、殆ど重量が変化せず、従って、その中に含まれているＣａＯが吸湿せず、二酸化炭素とも反応しないことを見出した。また、この焼結体は強度も大きく、容易に崩壊しないことを見出した。 The inventor mixed 70 parts by weight of magnesium oxide MgO, 25 parts of calcium oxide CaO and 5 parts of iron oxide FeO to make a mixture, pulverized the mixture, and obtained powder was 1400 ° C. The sintered body was made by heating to a temperature of Then, this sintered body was left in the air and the change in weight was observed. As a result, it was found that even if this sintered body was left for 6 months, the weight hardly changed, and therefore CaO contained therein did not absorb moisture and did not react with carbon dioxide. It was also found that this sintered body has high strength and does not easily collapse.
しかも、この焼結体は溶鋼に溶解し易く、また、水分含有量も少なく、さらに炉壁保護材としての良好な性能を保持していることを見出した。この発明は、このような知見に基づいて完成されたものである。
この発明は、重量を基準として、酸化マグネシウムＭｇＯが酸化カルシウムＣａＯよりも多く含まれている原材料に、酸化カルシウムより少ない量の酸化鉄ＦｅＯを加えて混合物とし、この混合物の粉末をブリケット状に成形し、成形物を焼成して焼結体とした物を炉壁保護材として使用することを骨子とするものである。
In addition, the present inventors have found that this sintered body is easily dissolved in molten steel, has a low water content, and maintains good performance as a furnace wall protective material. The present invention has been completed based on such knowledge.
In this invention, based on weight, raw material containing magnesium oxide MgO more than calcium oxide CaO is added to iron oxide FeO in a smaller amount than calcium oxide to form a mixture, and the powder of this mixture is formed into a briquette shape. However, the main point is to use a sintered product obtained by firing the molded product as a furnace wall protective material.
この炉壁保護材では、ＣａＯの融点がＭｇＯの融点よりも高いため、ＣａＯがＭｇＯに対して多くなると焼結体が強固でなくなり、またＦｅＯがＣａＯに対して極端に少ないときにはＦｅＯの効果が顕著に現われない。そのために加えるべきＣａＯとＦｅＯとにはそれぞれ限界を設ける必要があることが判明した。そこでその混合割合について種々実験を試みた結果、三者の割合は、重量でＭｇＯを６０〜８０％とし、ＣａＯを５〜３０％とし、ＦｅＯを０．５〜１０％とすることが適していることを見出した。 In this furnace wall protective material, the melting point of CaO is higher than the melting point of MgO. Therefore, when CaO increases with respect to MgO, the sintered body becomes not strong, and when FeO is extremely small with respect to CaO, the effect of FeO is obtained. Does not appear prominently. Therefore, it has been found that it is necessary to provide a limit to each of CaO and FeO to be added. Accordingly, as a result of various experiments on the mixing ratio, it is suitable that the ratio of the three is 60 to 80% MgO, 5 to 30% CaO, and 0.5 to 10% FeO. I found out.
かくして、この発明はマグネシウム含有化合物、カルシウム含有化合物及び鉄含有化合物を混合し、この混合物ではマグネシウム、カルシウム及び鉄がそれぞれ酸化マグネシウムＭｇＯ、酸化カルシウムＣａＯ及び酸化鉄ＦｅＯに換算して、重量で６０〜８０％、５〜３０％及び０．５〜１０％含まれているように調整し、この混合物の粉末をブリケットに成形し、焼成して焼結体にしたことを特徴とする製鋼用の炉壁保護材を提供するものである。 Thus, in the present invention, a magnesium-containing compound, a calcium-containing compound, and an iron-containing compound are mixed. In this mixture, magnesium, calcium, and iron are converted into magnesium oxide MgO, calcium oxide CaO, and iron oxide FeO, respectively. 80%, 5-30% and 0.5-10%, a steelmaking furnace characterized in that the powder of this mixture is formed into a briquette and fired into a sintered body A wall protection material is provided.
また、この発明は、炉壁保護材の製造方法を提供するものである。その製造方法は、マグネシウム含有化合物、カルシウム含有化合物及び鉄含有化合物を混合し、その混合物中ではマグネシウム、カルシウム及び鉄が、それぞれ酸化マグネシウムＭｇＯ、酸化カルシウムＣａＯ及び酸化鉄ＦｅＯに換算して、重量でそれぞれ６０〜８０％、５〜３０％及び０．５〜１０％となるように調整し、この混合物を粉砕して得られた粉末をブリケットに成形し、成形体を１２００〜１５５０℃の温度で焼成して、焼結体とすることを特徴とするものである。 Moreover, this invention provides the manufacturing method of a furnace wall protective material. The manufacturing method mixes a magnesium-containing compound, a calcium-containing compound, and an iron-containing compound, and magnesium, calcium, and iron are converted into magnesium oxide MgO, calcium oxide CaO, and iron oxide FeO, respectively, by weight in the mixture. The powders obtained by pulverizing this mixture were formed into briquettes, and the compacts were formed at a temperature of 1200 to 1550 ° C., adjusted to 60 to 80%, 5 to 30% and 0.5 to 10%, respectively. It is characterized by firing into a sintered body.
上記の比率は、マグネシウム、カルシウム及び鉄の相対的な比率を規定したものであって、炉壁保護材全体を基準とした含有率を規定したものではない。その理由は炉壁保護材は上記三者のほかにＳｉＯ2などの成分を含むことが許されるからである。 The above ratio defines the relative ratio of magnesium, calcium, and iron, and does not define the content based on the entire furnace wall protective material. The reason for this is that the furnace wall protective material is allowed to contain components such as SiO 2 in addition to the above three components.
この発明に係る炉壁保護材では、酸化マグネシウムＭｇＯと酸化カルシウムＣａＯとが混在している原材料に酸化鉄ＦｅＯを加えて焼成するから、ＦｅＯはＣａＯと結合してＣａＯ・ＦｅＯ又はＣａＯ・Ｆｅ2Ｏ3の形態となる。このＣａＯ・ＦｅＯ又はＣａＯ・Ｆｅ2Ｏ3はＣａＯよりも水及び二酸化炭素との親和性が弱く、しかも加熱されると流動し易いので、ＣａＯ・ＦｅＯ又はＣａＯ・Ｆｅ2Ｏ3がＭｇＯ及びＣａＯの表面を覆うこととなり、ＣａＯの水及び二酸化炭素との反応性が押さえられる。またＭｇＯはＣａＯよりも水及び二酸化炭素との親和性が弱いところ、重量でＭｇＯがＣａＯよりも多く含まれているから、少量のＦｅＯを加えただけでＣａＯの水及び二酸化炭素との反応性が押さえられる。従って、この炉壁保護材は製造後に長期間放置しても、貯蔵中に変化し難い。その結果、長い可使期間を持つことになる。 In the furnace wall protective material according to the present invention, since iron oxide FeO is added to the raw material in which magnesium oxide MgO and calcium oxide CaO are mixed and fired, FeO is combined with CaO and combined with CaO · FeO or CaO · Fe 2. O 3 form. Since this CaO.FeO or CaO.Fe 2 O 3 has a weaker affinity with water and carbon dioxide than CaO and is easy to flow when heated, CaO.FeO or CaO.Fe 2 O 3 is MgO and CaO. The reactivity of CaO with water and carbon dioxide is suppressed. Since MgO has a weaker affinity for water and carbon dioxide than CaO, it contains more MgO than CaO by weight, so the reactivity of CaO with water and carbon dioxide can be achieved by adding a small amount of FeO. Is suppressed. Therefore, even if this furnace wall protective material is left for a long time after production, it does not easily change during storage. As a result, it has a long pot life.
この発明では、酸化マグネシウム、酸化カルシウム及び酸化鉄を材料として用いる。それらの材料は化学的に純粋なものであってもよいが、またその他の介在物を含んだものであってもよい。例えば材料としてマグネシウム含有鉱石、カルシウム含有鉱石及び鉄含有鉱石を用いることができる。 In the present invention, magnesium oxide, calcium oxide and iron oxide are used as materials. These materials may be chemically pure or may contain other inclusions. For example, magnesium-containing ore, calcium-containing ore and iron-containing ore can be used as materials.
これらの鉱石や介在物を含んだ材料を使用する場合には、予めその中に含まれるマグネシウム分、カルシウム分及び鉄分を測定しておくことが望ましい。また、それらの成分はこれを酸化マグネシウム、酸化カルシウム及び酸化鉄ＦｅＯに換算しておくことが好ましい。それはこれらの材料を混合したあとで、混合物中にこれらの成分が酸化マグネシウム、酸化カルシウム及び酸化鉄に換算して特定の比率で含まれているように調整するのに好都合だからである。 When using materials containing these ores and inclusions, it is desirable to measure the magnesium content, calcium content and iron content contained therein in advance. Further, these components are preferably converted into magnesium oxide, calcium oxide and iron oxide FeO. This is because, after mixing these materials, it is convenient to adjust the mixture so that these components are contained in a specific ratio in terms of magnesium oxide, calcium oxide and iron oxide.
マグネシウム含有の鉱石としては前述のドロマイトのほかに、マグネサイトやブルーサイトが知られている。ところが、これらの鉱石のうち１つを単独で焼成しただけでは、この発明が規定するような割合でＭｇＯ、ＣａＯ及びＦｅＯが存在している混合物は得られない。その理由は次のとおりである。 In addition to the aforementioned dolomite, magnesite and brucite are known as magnesium-containing ores. However, a mixture containing MgO, CaO and FeO in a proportion as defined by the present invention cannot be obtained by merely firing one of these ores alone. The reason is as follows.
ドロマイトは前述のように、理想化学組成がＣａＣＯ3とＭｇＣＯ3との複塩とされているから、これを焼成すればＣａＯとＭｇＯとが等モル生じる筈であり、この発明のようにＭｇＯがＣａＯより多い混合物は得られない。ドロマイトの実際の分析値は、一例ではＣａＯが２９．９０、ＭｇＯが２２．２１、ＦｅＯが０．０８、ＣＯ2が４７．７７とされ、他の例ではＣａＯが３１．９７、ＭｇＯが１９．４２、ＦｅＯが１．０３、ＣＯ2が４７．１８、不溶物が１．２５％とされているから、ドロマイトを単独で焼成したのでは決してこの発明が規定する混合物は得られない。 As described above, dolomite has an ideal chemical composition of a double salt of CaCO 3 and MgCO 3, and if this is fired, CaO and MgO should be formed in an equimolar amount. A mixture greater than CaO is not obtained. The actual analytical values of dolomite are 29.90 for CaO, 22.21 for MgO, 0.08 for FeO and 47.77 for CO 2 in one example, and 31.97 for CaO and 19 for MgO. .42, FeO 1.03, CO 2 47.18, and insoluble matter 1.25%, calcination of dolomite alone never yields a mixture defined by the present invention.
マグネサイトは理想化学組成がＭｇＣＯ3とされているから、これを焼成するとＭｇＯとなる。ところが、実際のマグネサイトは、これを分析するとＭｇＯが４０．２８、ＣａＯが４．６１、Ｆｅ2Ｏ3が０．４５、Ａｌ2Ｏ3が０．２２、ＳｉＯ2が３．４５の割合で含まれている、と報告されている。従って、これを焼成すると、ＭｇＯのほかにＣａＯとＦｅＯとを含むものが得られるが、ＣａＯの量はＭｇＯの量の０．１１倍にあたり、この発明が規定する範囲内にない。ＦｅＯはＣａＯの１０分の１以下の僅かな量が含まれるに過ぎない。従って、マグネサイトを単独で焼成しただけでは、この発明が規定する混合物は得られない。 Since magnesite has an ideal chemical composition of MgCO 3 , it becomes MgO when fired. However, when analyzing actual magnesite, the ratio of MgO is 40.28, CaO is 4.61, Fe 2 O 3 is 0.45, Al 2 O 3 is 0.22, and SiO 2 is 3.45. It is reported that it is included. Accordingly, when this is fired, a material containing CaO and FeO in addition to MgO is obtained, but the amount of CaO is 0.11 times the amount of MgO and is not within the range specified by the present invention. FeO contains only a small amount of 1/10 or less of CaO. Therefore, the mixture defined by the present invention cannot be obtained by merely firing magnesite alone.
ブルーサイトは理想化学組成がＭｇ(ＯＨ)2とされているから、これを焼成するとＭｇＯとなる。ところが、ブルーサイトを分析した例では、ＭｇＯが６２．９２、ＳｉＯ2が１．４５、Ａｌ2Ｏ3＋Ｆｅ2Ｏ3が１．２０、ＣａＯが２．６７、ＭｎＯが０．０７含まれ、灼熱減量が３１．７５％とされている。従ってブルーサイトを焼成すると、ＭｇＯのほかにＣａＯとＦｅＯとが含まれたものが得られる。ところがＣａＯはＭｇＯの４％程度の僅かな量であり、ＦｅＯはＣａＯの２分の１以下の僅かな量である。従って、ブルーサイトを単独で焼成したのでは、この発明が規定する混合物は得られない。 Since brucite has an ideal chemical composition of Mg (OH) 2 , it becomes MgO when fired. However, in an example of analyzing brucite, MgO is 62.92, SiO 2 is 1.45, Al 2 O 3 + Fe 2 O 3 is 1.20, CaO is 2.67, and MnO is 0.07. The loss on ignition is 31.75%. Accordingly, when brucite is fired, a material containing CaO and FeO in addition to MgO is obtained. However, CaO is a slight amount of about 4% of MgO, and FeO is a small amount of 1/2 or less of CaO. Therefore, when brucite is baked alone, the mixture defined by the present invention cannot be obtained.
このように、この発明が規定する混合物はマグネシウムを含む鉱石を単独で焼成したのでは得られない。従って、この混合物を得るためには、これらマグネシウム含有鉱石に他の化合物又は鉱石を特定の割合で混合しなければならない。 As described above, the mixture defined by the present invention cannot be obtained by firing an ore containing magnesium alone. Therefore, in order to obtain this mixture, other compounds or ores must be mixed with these magnesium-containing ores at a specific ratio.
カルシウム含有鉱石としては石灰石を用いる。石灰石は理想化学組成がＣａＣＯ3とされているから、これを焼成すればＣａＯを生成する筈である。石灰石を分析した結果によれば、石灰石はＣａＯが５４．６３、ＭｇＯが０．８４、ＳｉＯ2が０．６４、Ｆｅ2Ｏ3が０．４３、Ａｌ2Ｏ3が０．４３、灼熱減量が４３．２％とされているから、ＭｇＯやＦｅ2Ｏ3を極めて僅か含むだけである。 Limestone is used as the calcium-containing ore. Since limestone has an ideal chemical composition of CaCO 3 , if it is fired, it should generate CaO. According to the result of analyzing limestone, CaO is 54.63, MgO is 0.84, SiO 2 is 0.64, Fe 2 O 3 is 0.43, Al 2 O 3 is 0.43, and loss on ignition is reduced. Is 43.2%, it contains very little MgO or Fe 2 O 3 .
酸化鉄としては専らミルスケールを用いる。ミルスケールは高温の鉄を高温の空気中に曝したとき、鉄の表面に生じる酸化鉄の厚い層である。鉄の鍛造のときに鉄の表面に生成されるものである。
この発明では、原料として鉱石を用いるときは、前述のように、各鉱石についてＭｇＯ、ＣａＯ及びＦｅＯの含有量を分析しておき、各鉱石を混合した場合、混合物中のＭｇＯ、ＣａＯ及びＦｅＯの含まれる割合が規定の範囲、すなわち、重量でそれぞれ６０〜８０％、５〜３０％及び０．５〜１０％の範囲内に納まるようにする。
Mill scale is exclusively used as iron oxide. Mill scale is a thick layer of iron oxide that forms on the surface of hot iron when it is exposed to hot air. It is generated on the surface of iron during iron forging.
In this invention, when using ore as a raw material, as described above, the contents of MgO, CaO and FeO are analyzed for each ore, and when each ore is mixed, MgO, CaO and FeO in the mixture are analyzed. The contained ratio is set within a specified range, that is, within a range of 60 to 80%, 5 to 30%, and 0.5 to 10%, respectively, by weight.
この発明が規定するＭｇＯとＣａＯとＦｅＯとの混合割合の中ではＭｇＯを６５〜７５％、ＣａＯを２０〜３０％、ＦｅＯを３〜７％とすることが好ましい。さらに好ましいのはＭｇＯを７０％、ＣａＯを２５％、ＦｅＯを５％とすることである。
この発明では、マグネシウム含有化合物、カルシウム含有化合物及び鉄含有化合物の混合物を粉砕して粉末とする。粉末の程度は１６〜６０メッシュの篩を通過できる程度とすることが好ましい。
In the mixing ratio of MgO, CaO and FeO defined by the present invention, it is preferable that MgO is 65 to 75%, CaO is 20 to 30% and FeO is 3 to 7%. More preferably, MgO is 70%, CaO is 25%, and FeO is 5%.
In the present invention, a mixture of a magnesium-containing compound, a calcium-containing compound and an iron-containing compound is pulverized into a powder. The degree of powder is preferably such that it can pass through a sieve of 16 to 60 mesh.
この発明では、上記の粉末をブリケット状に成形する。成形のために結合剤又は粘結剤を用いることができる。結合剤又は粘結剤としては生石灰を用いることができる。ブリケットの大きさとしては直径が数ｃｍの球又は円板状とすることが好ましい。
この発明ではこうしてブリケットに成形したものを焼成する。焼成温度は１２００〜１５５０℃の範囲内とする。そのうちでは１３００〜１４００℃の温度で焼成することが好ましい。
In the present invention, the above powder is formed into a briquette. Binders or binders can be used for molding. Quick lime can be used as the binder or binder. The size of the briquette is preferably a sphere or disk having a diameter of several centimeters.
In the present invention, the briquette thus formed is fired. The firing temperature is in the range of 1200 to 1550 ° C. Of these, firing at a temperature of 1300 to 1400 ° C. is preferred.
この発明に係る炉壁保護材は、重量でＭｇＯが６０〜８０％、ＣａＯが５〜３０％、ＦｅＯが０．５〜１０％含まれているものを１２００〜１５５０℃の温度で焼成したので、ＣａＯとＦｅＯとが結合して、ＣａＯ・ＦｅＯ又はＣａＯ・Ｆｅ2Ｏ3が生成され、これがＭｇＯ・ＣａＯの表面を覆うこととなるので、ＣａＯの反応性が押さえられる。従って、この焼結体は可使期間が長期にわたる。ＭｇＯボールでは可使期間が３ヶ月程度であるのに、この発明に係る炉壁保護材では可使期間が６〜１２ヶ月にも延長される。 Since the furnace wall protective material according to the present invention is fired at a temperature of 1200 to 1550 ° C. containing 60 to 80% MgO, 5 to 30% CaO and 0.5 to 10% FeO by weight. , CaO and FeO are combined to produce CaO.FeO or CaO.Fe 2 O 3 , which covers the surface of MgO.CaO, so that the reactivity of CaO is suppressed. Therefore, this sintered body has a long service life. In MgO balls, the pot life is about 3 months, but in the furnace wall protective material according to the present invention, the pot life is extended to 6 to 12 months.
また、この発明に係る炉壁保護材は強度が高い。従来のＭｇＯボールでは吸湿などのために炉壁保護材が劣化して強度が低下するが、この発明の炉壁保護材ではＣａＯ・ＦｅＯ又はＣａＯ・Ｆｅ2Ｏ3が表面に膜を形成しているために強度が高い。また、焼結体となっているために一層強度が高くなっている。従って、取扱い中に粉砕され難い。 Moreover, the furnace wall protective material according to the present invention has high strength. In conventional MgO ball strength furnace wall protective material is deteriorated due to the moisture absorption is reduced but, CaO · FeO or CaO · Fe 2 O 3 in the oven wall protective material of the present invention may form a film on the surface Therefore, the strength is high. Moreover, since it is a sintered body, the strength is further increased. Therefore, it is difficult to be crushed during handling.
この発明では１３００〜１５００℃の温度で焼成して焼結体にして、得られた焼結体を空気中に放置したとき、粉化したり吸湿したりすることをより完全に防止するために、また焼成温度を低下させるために、酸化鉄ＦｅＯのほかに酸化アルミニウムＡｌ2Ｏ3を添加することができる。酸化アルミニウムを酸化鉄とほぼ等量、すなわち１〜１０％添加すると、焼成が容易となり、１４００℃以下の比較的低い温度で焼成することができることとなる。Ａｌ2Ｏ3を加えると、Ａｌ2Ｏ3はＦｅＯと同様にＣａＯ・Ａｌ2Ｏ3を生成し、これがＭｇＯ・ＣａＯの表面を覆うに至るので、ＣａＯの反応性が抑制されると考えられる。Ａｌ2Ｏ3を添加して得られた焼結体は、より長期間大気中に放置しても、水分吸収により粉化することがなくなっている。 In this invention, in order to more completely prevent pulverization and moisture absorption when the sintered body obtained by firing at a temperature of 1300 to 1500 ° C. is left in the air, In order to lower the firing temperature, aluminum oxide Al 2 O 3 can be added in addition to iron oxide FeO. When aluminum oxide is added in substantially the same amount as iron oxide, that is, 1 to 10%, firing is facilitated and firing can be performed at a relatively low temperature of 1400 ° C. or lower. When Al 2 O 3 is added, Al 2 O 3 generates CaO · Al 2 O 3 like FeO, and this covers the surface of MgO · CaO, so the reactivity of CaO is considered to be suppressed. . The sintered body obtained by adding Al 2 O 3 does not pulverize due to moisture absorption even when left in the atmosphere for a longer period of time.
さらに、この発明に係る炉壁保護材では焼結させたために付着水と結晶水が少なくなっているので熱エネルギーの損失が少なく、従って添加時に溶湯の温度低下が少なく、また水素により鋼が劣化される危険性も低減させることができる。
以下に実施例と比較例とを挙げて、この発明のすぐれている所以を説明する。
Furthermore, since the furnace wall protective material according to the present invention is sintered, the amount of adhering water and crystallization water is small, so there is little loss of thermal energy, so there is little temperature drop of the molten metal when added, and the steel is deteriorated by hydrogen. The risk of being lost can also be reduced.
The reason why the present invention is excellent will be described below with reference to examples and comparative examples.
実施例１
この実施例では何れも化学的にほぼ純粋な材料を使用して、重量でＭｇＯを６５％、ＣａＯを３０％、ＦｅＯを５％の割合で混合した混合物を作り、これを粉砕して６０メッシュ通過の粉末とした。この粉末にバインダーとして１％の消石灰の水溶液を混合物に対して２％加え、これを型内に充填し圧縮して直径３０ｍｍ、厚み２５ｍｍの円板状に成形した。この成形体を１４００℃の温度で６０分間焼成してブリケットとした。
Example 1
In this example, a chemically nearly pure material was used to make a mixture of 65% MgO, 30% CaO and 5% FeO by weight, and this was pulverized to 60 mesh. It was a passing powder. A 2% aqueous solution of 1% slaked lime as a binder was added to this powder, filled in a mold, and compressed to form a disk having a diameter of 30 mm and a thickness of 25 mm. This molded body was fired at a temperature of 1400 ° C. for 60 minutes to form a briquette.
このブリケットはこれを大気中に放置したところ、１２ヶ月経過しても重量の増加がなく、外観上も粉化した形跡は全く見られなかった。また、これを炉壁保護材として転炉内での製鋼に使用したところ、溶鋼中に容易に溶解した。溶鋼を流出させたあとで転炉の壁面を調査したところ、壁面は殆ど損傷を受けていなかった。従って、この焼結体は炉壁の保護材としての機能を充分に持ったものと認められた。 When this briquette was left in the atmosphere, there was no increase in weight even after 12 months had passed, and no evidence of pulverization was observed. Moreover, when this was used for steel making in a converter as a furnace wall protective material, it melt | dissolved easily in molten steel. After investigating the molten steel, the wall surface of the converter was examined, and the wall surface was hardly damaged. Therefore, this sintered body was recognized as having sufficient function as a furnace wall protective material.
他方、比較のためにＭｇＯボールを同じ環境下の大気中に放置したところ３ヶ月で粉化した。これを炉壁保護材として使用したところ、吸湿していたために熱エネルギーの損失が大きかった。 On the other hand, when the MgO balls were left in the atmosphere under the same environment for comparison, they were pulverized in 3 months. When this was used as a furnace wall protective material, the loss of heat energy was large due to moisture absorption.
実施例２
この実施例では実施例１と同じく何れも化学的にほぼ純粋なＭｇＯ、ＣａＯ及びＦｅＯを用いた。
重量でＭｇＯを７５％、ＣａＯを２０％、ＦｅＯを５％の割合で混合して混合物を作った。この混合物を実施例１と同様に処理してブリケットを作った。このブリケットは、これを大気中に放置したところ、１２ヶ月経過しても重量の増加がなく、外観上も粉化した形跡は全く見られなかった。また、これを炉壁保護材として転炉内で製鋼したところ、溶鋼中に容易に溶解して、炉壁保護材として満足なものであった。
Example 2
In this example, chemically almost pure MgO, CaO and FeO were used in the same manner as in Example 1.
A mixture was prepared by mixing 75% MgO, 20% CaO and 5% FeO by weight. This mixture was processed as in Example 1 to make briquettes. When this briquette was left in the atmosphere, there was no increase in weight even after 12 months, and no evidence of powdered appearance was observed at all. Moreover, when this was steel-made in a converter as a furnace wall protective material, it melt | dissolved easily in molten steel and was satisfactory as a furnace wall protective material.
実施例３
この実施例ではＭｇ源としてマグネサイトを用い、Ｃａ源として石灰石を用い、Ｆｅ源としてミルスケールを用いた。マグネサイトとしては、重量％でＭｇＯを４０．２８、ＣａＯを４．６１、Ｆｅ2Ｏ3を０．４５、Ａｌ2Ｏ3を０．２２、ＳｉＯ2を３．４５含むものを用いた。
Example 3
In this example, magnesite was used as the Mg source, limestone was used as the Ca source, and mill scale was used as the Fe source. The magnesite, the MgO by weight percent 40.28, 4.61 and CaO, Fe 2 O 3 and 0.45, the Al 2 O 3 0.22, was used as the a SiO 2 containing 3.45.
上記のマグネサイト１．３６ｋｇ、石灰石０．５４ｋｇ、ミルスケール０．１ｋｇを混合し、ＭｇＯとしてはほぼ７０％、ＣａＯとしては２５％、ＦｅＯとしては５％を含み、そのほか微量のＡｌ2Ｏ3を含む混合物を得た。この混合物を粉砕して６０メッシュ通過の粉末とし、バインダーとして１％の消石灰の水溶液を混合物に対して２％の割合で加え、これを直径３０ｍｍ、厚み２５ｍｍのブリケットに成形した。この成形体を１４００℃で６０分間焼成して焼結体を得た。この焼結体は湿度９０％、温度８０℃の試験器の中に４８時間放置しても、重量変化がなくて粉化が全く認められなかった。また、これを転炉内で実際に炉壁保護材として使用したところ、焼結体は溶鋼によく溶解した。また、溶鋼流出後に炉壁を調査したところ、炉壁に損傷が認められないので、この焼結体は炉壁保護材として適したものであることを認めた。 The above magnesite 1.36 kg, limestone 0.54 kg, and mill scale 0.1 kg are mixed, and MgO contains approximately 70%, CaO contains 25%, FeO contains 5%, and a small amount of Al 2 O 3. A mixture containing was obtained. The mixture was pulverized to obtain a 60-mesh powder, and a 1% aqueous solution of slaked lime was added as a binder at a ratio of 2% to the mixture, which was formed into a briquette having a diameter of 30 mm and a thickness of 25 mm. This molded body was fired at 1400 ° C. for 60 minutes to obtain a sintered body. Even when this sintered body was left in a tester having a humidity of 90% and a temperature of 80 ° C. for 48 hours, there was no change in weight and no powdering was observed. Moreover, when this was actually used in the converter as a furnace wall protective material, the sintered body was well dissolved in the molten steel. Further, when the furnace wall was investigated after the molten steel flowed out, no damage was observed in the furnace wall, and it was confirmed that this sintered body was suitable as a furnace wall protective material.
実施例４
この実施例では、実施例３で用いたマグネサイトと石灰石とミルスケールを用い、これにＡｌ2Ｏ3としてアルミ灰を加えて、Ａｌ2Ｏ3含有量の多い炉壁保護材を作った。
具体的にはマグネサイト１．４ｋｇ、石灰石０．４ｋｇ、ミルスケール０．１ｋｇ及びアルミ灰０．１ｋｇを混合して、重量で大凡ＭｇＯが７０％、ＣａＯが２０％、ＦｅＯが５％及びＡｌ2Ｏ3が５％の混合物を作った。この混合物を粉砕して６０メッシュの篩を通過する粉末を作り、この粉末にバインダーとして１％の消石灰の水溶液を２％の割合で加え、これを直径３０ｍｍ、厚み２５ｍｍのブリケットに成形した。この成形体を焼成したところ、この成形体は、実施例３で得た成形体よりも焼結が容易で、１３００℃で焼結体を得ることができた。
Example 4
In this embodiment, using magnesite and limestone and mill scale used in Example 3, this by the aluminum ash added as Al 2 O 3, to make a lot of content of Al 2 O 3 oven wall protective material.
Specifically, 1.4 kg of magnesite, 0.4 kg of limestone, 0.1 kg of mill scale and 0.1 kg of aluminum ash are mixed, and the weight is approximately 70% MgO, 20% CaO, 5% FeO and Al. A mixture of 5% 2 O 3 was made. The mixture was pulverized to make a powder that passed through a 60-mesh sieve. A 1% aqueous solution of slaked lime was added to the powder as a binder at a rate of 2%, and this was formed into a briquette having a diameter of 30 mm and a thickness of 25 mm. When this molded body was fired, the molded body was easier to sinter than the molded body obtained in Example 3, and a sintered body could be obtained at 1300 ° C.
この焼結体は湿度９０％、温度８０℃の試験器の中に３日間放置しても、重量変化がなく、また粉化が全く認められなかった。これにより、この焼結体は実施例３の焼結体よりも低温で焼結でき、吸湿性が少なく、従って一層優れていることが確認された。また、この焼結体を転炉内で溶鋼に添加したところ、焼結体は溶鋼によく溶解した。溶鋼を流出させたあとで炉の壁面を調査したところ、炉壁に損傷が認められなかった。従って、この焼結体は炉壁保護材として適したものと認められた。 Even if this sintered body was left in a tester having a humidity of 90% and a temperature of 80 ° C. for 3 days, there was no change in weight and no powdering was observed. Thereby, it was confirmed that this sintered body could be sintered at a lower temperature than the sintered body of Example 3, had less hygroscopicity, and therefore was superior. Further, when this sintered body was added to the molten steel in the converter, the sintered body was well dissolved in the molten steel. After investigating the molten steel, the wall surface of the furnace was examined, and no damage was found on the furnace wall. Therefore, this sintered body was recognized as being suitable as a furnace wall protective material.
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