JP2022065401A - Castable refractory and molten steel ladle using the same - Google Patents
Castable refractory and molten steel ladle using the same Download PDFInfo
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- JP2022065401A JP2022065401A JP2020173973A JP2020173973A JP2022065401A JP 2022065401 A JP2022065401 A JP 2022065401A JP 2020173973 A JP2020173973 A JP 2020173973A JP 2020173973 A JP2020173973 A JP 2020173973A JP 2022065401 A JP2022065401 A JP 2022065401A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 18
- 239000010959 steel Substances 0.000 title claims abstract description 18
- 239000004568 cement Substances 0.000 claims abstract description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005084 Strontium aluminate Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 9
- 239000011029 spinel Substances 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 26
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 26
- 239000011819 refractory material Substances 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 34
- 229910002804 graphite Inorganic materials 0.000 description 18
- 239000010439 graphite Substances 0.000 description 18
- 239000006229 carbon black Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011295 pitch Substances 0.000 description 9
- 238000010276 construction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000013003 hot bending Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- -1 SrAl 2 O 4 Chemical compound 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
Description
本発明は、製鉄所内で使用されるキャスタブル耐火物およびそれを用いた溶鋼鍋に関する。 The present invention relates to a castable refractory used in a steel mill and a molten steel pan using the same.
近年、製鉄所で使用される耐火物に占めるキャスタブル耐火物の使用比率が増大している。中でも製鋼段階での二次精錬で使用される溶鋼鍋の内張耐火物として、製鉄所内で原料と水を混合して施工するキャスタブル耐火物が広く使用されている。 In recent years, the ratio of castable refractories to the refractories used in steelworks has increased. Among them, as a refractory lining of a molten steel pot used in secondary refractory at the steelmaking stage, a castable refractory that is constructed by mixing raw materials and water in a steelmaking plant is widely used.
溶鋼鍋内張耐火物の損傷形態としては、熱衝撃やスラグ浸透によるスポーリング、スラグによる侵食によるものが挙げられる。キャスタブル耐火物は、通常、結合剤としてＣａＯを含有するアルミナセメントを含有しているものが多いが、ＣａＯ成分は高温ではＡｌ２Ｏ３、ＭｇＯ、ＳｉＯ２とともに低融物を生成し、熱間強度低下や化学的侵食をもたらす。 Examples of the damage form of the refractory material lining the molten steel pot include those caused by thermal shock, spalling due to slag infiltration, and erosion caused by slag. Most castable refractories usually contain alumina cement containing CaO as a binder, but the CaO component produces a low melt together with Al 2 O 3 , MgO, and SiO 2 at high temperatures, and is hot. It causes a decrease in strength and chemical erosion.
これに対し、特許文献1および特許文献２には、ＳｒＡｌ２Ｏ４等のストロンチウムアルミネートを含有するキャスタブル耐火物用結合剤と、該結合剤を使用したキャスタブル耐火物に関する技術が提案されている。 On the other hand, Patent Document 1 and Patent Document 2 propose a binder for a castable refractory containing strontium aluminate such as SrAl 2 O 4 , and a technique for a castable refractory using the binder. ..
しかしながら、特許文献１および特許文献２で開示されるようなストロンチウムアルミネートを含有する結合剤は、ＣａＯが固溶している場合、大量に添加した場合には使用中に低融物を生成するのが問題であった。 However, a binder containing strontium aluminate as disclosed in Patent Document 1 and Patent Document 2 produces a low melt during use when CaO is dissolved in a solid solution and when added in a large amount. Was the problem.
本発明の目的は、前記課題を解決して、使用中に低融物の生成がない施工性のよいキャスタブル耐火物およびそれを用いた溶鋼鍋を提供することにある。 An object of the present invention is to solve the above-mentioned problems and to provide a castable refractory having good workability and a molten steel pot using the same, which does not generate low melt during use.
本発明者らは、ＳｒＯ－Ａｌ２Ｏ３－ＳｉＯ２系およびＳｒＯ－ＭｇＯ－Ａｌ２Ｏ３系の鉱物が１６５０℃でも溶融しないこと、および、カーボンを含有するキャスタブル耐火物では、カルシウムアルミネートを含有するアルミナセメントではなくストロンチウムアルミネートを含有するセメントを使用することで、熱処理後の亀裂を抑制できること、を確認し、本発明を開発するに至ったものである。 The present inventors do not melt the SrO-Al 2 O 3 -SiO 2 system and SrO-MgO-Al 2 O 3 system minerals even at 1650 ° C., and in castable refractories containing carbon, calcium aluminate. It was confirmed that cracks after heat treatment can be suppressed by using a cement containing strontium aluminate instead of an alumina cement containing, and the present invention has been developed.
即ち、本発明は、アルミナ、カーボンおよびマグネシアを含有するキャスタブル耐火物、または、アルミナ、カーボンおよびスピネルを含有するキャスタブル耐火物において、ストロンチウムアルミネートを含有するセメントを７質量％以上２０質量％以下、および分散剤を含有し、分散剤を除く原料中のＣａＯの含有率が０．３質量％以下であることを特徴とするキャスタブル耐火物である。 That is, in the present invention, in a castable refractory containing alumina, carbon and magnesia, or a castable refractory containing alumina, carbon and spinel, the cement containing strontium aluminate is contained in an amount of 7% by mass or more and 20% by mass or less. It is a castable refractory that contains a dispersant and has a CaO content of 0.3% by mass or less in the raw material excluding the dispersant.
なお、前記のように構成される本発明に係るキャスタブル耐火物においては、
（１）前記ストロンチウムアルミネートを含有するセメントを１１量％以上２０質量％以下含有すること、
（２）前記ストロンチウムアルミネートを含有するセメントを１１質量％以上１４質量％以下含有すること、
がより好ましい解決手段となるものと考えられる。
In the castable refractory material according to the present invention configured as described above,
(1) The cement containing the strontium aluminumate should be contained in an amount of 11% by mass or more and 20% by mass or less.
(2) The cement containing the strontium aluminumate should be contained in an amount of 11% by mass or more and 14% by mass or less.
Is considered to be a more preferable solution.
また、本発明は、上述したキャスタブル耐火物を、内張耐火物として用いたことを特徴とする溶鋼鍋である。 Further, the present invention is a molten steel pan characterized in that the above-mentioned castable refractory is used as a lining refractory.
本発明に係るキャスタブル耐火物によれば、アルミナセメントに替えてストロンチウムアルミネートを含有するセメントを使用することで、セメント由来のＣａＯの含有が少なくなりＣａＯによる低融物の生成量が少なく、高い熱間強度と優れた耐食性を得られるようになった。また、分散剤を除く原料中のＣａＯ量を、０．３質量％以下にすることにより、耐食性を落とすことなく、高い熱間強度を得られるようになった。 According to the castable refractory material according to the present invention, by using a cement containing strontium aluminate instead of the alumina cement, the content of CaO derived from the cement is reduced, and the amount of low melt produced by CaO is small and high. It has become possible to obtain hot strength and excellent corrosion resistance. Further, by setting the amount of CaO in the raw material excluding the dispersant to 0.3% by mass or less, high hot strength can be obtained without deteriorating the corrosion resistance.
また、アルミナセメントは１４００℃以上の環境において、以下の（１）式：
ＣａＡｌ４Ｏ７＋４Ａｌ２Ｏ３→ＣａＡｌ１２Ｏ１９・・・（１）
の反応により体積膨張を生じる。カーボンを含有しないキャスタブル耐火物は１４００℃以上で焼結により収縮するが、カーボンを含有するキャスタブル耐火物ではカーボンが焼結を阻害するため、（１）式の反応により冷却後に線変化率が大きくなり、施工体に亀裂が生じることがある。アルミナセメントではなくストロンチウムアルミネートを含有するセメントを使用すれば、（１）式の反応が生じないので熱処理後も残存膨張は必要以上に大きくならず、施工体に亀裂が生じないという効果もある。
In addition, alumina cement has the following formula (1): in an environment of 1400 ° C or higher.
CaAl 4 O 7 + 4Al 2 O 3 → CaAl 12 O 19 ... (1)
Volume expansion occurs due to the reaction of. Castable refractories that do not contain carbon shrink at 1400 ° C or higher due to sintering, but in castable refractories that contain carbon, carbon inhibits sintering, so the rate of linear change after cooling is large due to the reaction of equation (1). As a result, cracks may occur in the construction body. If cement containing strontium aluminate is used instead of alumina cement, the reaction of equation (1) does not occur, so the residual expansion does not become larger than necessary even after heat treatment, and there is also the effect that cracks do not occur in the construction body. ..
さらに、本発明に係る溶鋼鍋では、上述した耐食性や熱間強度等に優れる本発明に係るキャスタブル耐火物を内張耐火物として用いるため、耐用性の高い溶鋼鍋を得ることができる。 Further, in the molten steel pan according to the present invention, since the castable refractory according to the present invention, which is excellent in corrosion resistance and hot strength, is used as the lining refractory, a molten steel pan having high durability can be obtained.
本発明に係るキャスタブル耐火物は、アルミナ、カーボンおよびマグネシアを含有するキャスタブル耐火物、または、アルミナ、カーボンおよびスピネルを含有するキャスタブル耐火物において、ストロンチウムアルミネートを含有するセメントを７質量％以上２０質量％以下、および分散剤を含有し、分散剤を除く原料中のＣａＯの含有率が０．３質量％以下であることを特徴としている。 The castable refractory according to the present invention is a castable refractory containing alumina, carbon and magnesia, or a castable refractory containing alumina, carbon and spinel, and contains 7% by mass or more and 20% by mass of cement containing strontium aluminate. % Or less, and the content of CaO in the raw material excluding the dispersant is 0.3% by mass or less.
本発明によれば、キャスタブル耐火物中のセメントをアルミナセメントに代えてストロンチウムアルミネートを含有するセメントにしたため、ＣａＯを含む低融物、例えば、１６００℃以下で溶融するＣａ２Ａｌ２ＳｉＯ７、ＣａＡｌ２ＳｉＯ６等の生成量が少なくなり、代わりに１６５０℃でも溶融しないＳｒＡｌ２Ｓｉ２Ｏ８、Ｓｒ０．９２Ｍｇ０．９１Ａｌ１０．０９Ｏ１７等を生成し、耐食性と熱間強度が向上した。また、ＣａＯ量を０．３質量％以下にすることにより、ＣａＯを含む上記の低融物の生成量が少なくなるため耐食性を落とすことなく、高い熱間強度を得られるようになった。さらに、上記（１）式の反応が生じないことにより、熱処理後に亀裂が発生しなくなった。 According to the present invention, since the cement in the castable refractory is replaced with an alumina cement to be a cement containing strontium aluminate, a low melt containing CaO, for example, Ca 2 Al 2 SiO 7 , which melts at 1600 ° C. or lower, is used. The amount of CaAl 2 SiO 6 produced is reduced, and instead SrAl 2 Si 2 O 8 and Sr 0.92 Mg 0.91 Al 10.09 O 17 that do not melt even at 1650 ° C are produced, resulting in corrosion resistance and hot strength. Has improved. Further, by setting the amount of CaO to 0.3% by mass or less, the amount of the above-mentioned low melt containing CaO is reduced, so that high hot strength can be obtained without deteriorating the corrosion resistance. Further, since the reaction of the above formula (1) did not occur, cracks did not occur after the heat treatment.
ストロンチウムアルミネートを含有するセメントは、キャスタブル耐火物に対し、７質量％以上２０質量％、好ましくは１１質量％以上２０質量％、より好ましくは１１質量％以上１４質量％含有する。ここで、ストロンチウムアルミネートを含有するセメントが７質量％未満では、脱枠に必要とされている強度を得られない。また、ストロンチウムアルミネートを含有するセメントが２０質量％を超えると、施工性が低下して施工に必要な水分量が増大し、見かけ気孔率増大をもたらす。また、分散剤以外の原料に対するＣａＯ含有量は０．３質量％以下とする。分散剤以外の原料に対するＣａＯ含有量が０．３質量％を超えると、耐食性、熱間強度の低下をもたらす。 The cement containing strontium aluminate contains 7% by mass or more and 20% by mass, preferably 11% by mass or more and 20% by mass, and more preferably 11% by mass or more and 14% by mass with respect to the castable refractory. Here, if the cement containing strontium aluminate is less than 7% by mass, the strength required for deframement cannot be obtained. Further, when the cement containing strontium aluminate exceeds 20% by mass, the workability is lowered, the amount of water required for the work is increased, and the apparent porosity is increased. The CaO content with respect to the raw materials other than the dispersant shall be 0.3% by mass or less. When the CaO content with respect to the raw materials other than the dispersant exceeds 0.3% by mass, the corrosion resistance and the hot strength are lowered.
セメント以外の原料として、耐火性原料としてアルミナ、カーボンおよびマグネシア、または、アルミナ、カーボンおよびスピネル、を含有する。ここで、カーボンとは、鱗状黒鉛、鱗片状黒鉛、土状黒鉛、人造黒鉛、ピッチ、カーボンブラック、無煙炭、コークスなどをいう。結合剤のストロンチウムアルミネートを含有するセメントについては、例えば、ＳｒＯ＝１７．２質量％、Ａｌ２Ｏ３＝７６．５質量％、ＣａＯ＝１．５質量％、ＳｉＯ２＝０．１質量％の市販品を使用することが出来る。結合剤としては、ストロンチウムアルミネートを含有するセメントに加えて、アルミナゾル、シリカゾルなどを併用して使用できる。その他、酸化防止剤として、金属シリコンなどの各種金属、炭化珪素、炭化ホウ素などの炭化物を含んでもよい。さらに、耐火性原料の一部として、５質量％以下程度であればシリカヒューム、粘土、を含んでもよい。以上の原料に加えて、ポリカルボン酸系、ポリエーテル系、ポリマー系、ナフタレンスルホン酸系などの各種分散剤、その他、キャスタブル耐火物に一般的に使用される各種添加剤を使用することができるものとする。 As a raw material other than cement, alumina, carbon and magnesia, or alumina, carbon and spinel are contained as refractory raw materials. Here, carbon refers to scaly graphite, scaly graphite, earthy graphite, artificial graphite, pitch, carbon black, anthracite, coke and the like. For cement containing the binder strontium aluminate, for example, SrO = 17.2% by mass, Al 2O 3 = 76.5% by mass, CaO = 1.5% by mass, SiO 2 = 0.1% by mass. Commercially available products can be used. As the binder, in addition to cement containing strontium aluminate, alumina sol, silica sol and the like can be used in combination. In addition, as the antioxidant, various metals such as metallic silicon and carbides such as silicon carbide and boron carbide may be contained. Further, silica fume and clay may be contained as a part of the refractory raw material as long as it is about 5% by mass or less. In addition to the above raw materials, various dispersants such as polycarboxylic acid-based, polyether-based, polymer-based, and naphthalene sulfonic acid-based, and various additives generally used for castable refractories can be used. It shall be.
本発明において、ストロンチウムアルミネートを含有するセメントおよび分散剤を除く原料中のＣａＯのそれぞれの含有量の他の組成の含有量は、一般的なキャスタブル耐火物で用いられるものと同様で、一例として以下の例が挙げられる。まず、アルミナ、カーボンおよびマグネシアを含むキャスタブル耐火物では、電融アルミナまたは焼結アルミナが３９質量％以上８５質量％以下、仮焼アルミナが２質量％以上２０質量％以下、カーボンが１質量％以上１０質量％以下、マグネシアが５質量％以上１０質量％以下、分散剤が０．０５質量％以上２．５質量％以下である。また、アルミナ、カーボンおよびスピネルを含むキャスタブル耐火物では、アルミナが１２質量％以上７３質量％以下、仮焼アルミナが２質量％以上２０質量％以下、カーボンが１質量％以上１０質量％以下、スピネルが１７質量％以上３７質量％以下、分散剤が０．０５質量％以上２．５質量％以下である。 In the present invention, the content of each of the CaO contents in the raw materials excluding the cement containing strontium aluminate and the dispersant is the same as that used in a general castable refractory, and as an example. The following examples are given. First, in castable refractory materials containing alumina, carbon and magnesia, fused alumina or sintered alumina is 39% by mass or more and 85% by mass or less, calcined alumina is 2% by mass or more and 20% by mass or less, and carbon is 1% by mass or more. It is 10% by mass or less, magnesia is 5% by mass or more and 10% by mass or less, and the dispersant is 0.05% by mass or more and 2.5% by mass or less. In the castable refractory material containing alumina, carbon and spinel, alumina is 12% by mass or more and 73% by mass or less, calcined alumina is 2% by mass or more and 20% by mass or less, carbon is 1% by mass or more and 10% by mass or less, and spinel. Is 17% by mass or more and 37% by mass or less, and the dispersant is 0.05% by mass or more and 2.5% by mass or less.
骨材のアルミナの一部に、粒径が細かい仮焼アルミナを使用することで、ストロンチウムアルミネートを含有するセメントを使用する際に、特に冬場など気温が低い場合において、施工後１日経過した時点での強度の向上が期待でき、好適である。 By using calcined alumina with a fine particle size as part of the alumina of the aggregate, one day has passed since the construction when using cement containing strontium aluminate, especially when the temperature is low such as in winter. It is suitable because it can be expected to improve the strength at the time point.
＜実施例１＞
以下の表１に、アルミナ－マグネシア－カーボンキャスタブル耐火物に、ストロンチウムアルミネートを含有するセメント（以下、ストロンチウムセメントという）を適用した本発明例１～７と比較例３、４、および、アルミナセメントを適用した比較例２、さらに、アルミナ－マグネシアキャスタブル耐火物に、アルミナセメントを適用した比較例１を示す。
<Example 1>
Table 1 below shows Examples 1 to 7 of the present invention, Comparative Examples 3, 4 and Alumina Cement in which cement containing strontium aluminate (hereinafter referred to as strontium cement) was applied to an alumina-magnesia-carbon castable refractory. 2 is further shown, and Comparative Example 1 in which alumina cement is applied to an alumina-magnesia castable refractory is shown.
本発明例１～４は、いずれも鱗状黒鉛５質量％の場合であって、本発明例１はストロンチウムセメント７質量％、本発明例２はストロンチウムセメント１１質量％、本発明例３はストロンチウムセメント１４質量％、本発明例４はストロンチウムセメント２０質量％を使用したアルミナ－マグネシア－カーボンキャスタブル耐火物である。本発明例５、本発明例６、本発明例７は、いずれもストロンチウムセメント７質量％の場合であって、本発明例５は鱗状黒鉛１質量％、本発明例６は鱗状黒鉛１０質量％、本発明例７はピッチ２．５質量％とカーボンブラック２．５質量％を使用したアルミナ－マグネシア－カーボンキャスタブル耐火物である。 Examples 1 to 4 of the present invention are all cases of scale graphite 5% by mass, Example 1 of the present invention is 7% by mass of strontium cement, Example 2 of the present invention is 11% by mass of strontium cement, and Example 3 of the present invention is strontium cement. Example 4 of the present invention is an alumina-magnesia-carbon castable refractory using 14% by mass and 20% by mass of strontium cement. Examples 5 of the present invention, Example 6 of the present invention, and Example 7 of the present invention are all cases of 7% by mass of strontium cement, 1% by mass of scaly graphite in Example 5 of the present invention, and 10% by mass of scaly graphite in Example 6 of the present invention. Example 7 of the present invention is an alumina-magnesia-carbon castable fireproof material using 2.5% by mass of pitch and 2.5% by mass of carbon black.
比較例１は、アルミナセメント７質量％を使用したアルミナ－マグネシアキャスタブル耐火物である。比較例２は、アルミナセメント７質量％を使用したアルミナ－マグネシア－カーボンキャスタブル耐火物である。比較例３は、ストロンチウムセメント量が本発明範囲より少ない６質量％を使用したアルミナ－マグネシア－カーボンキャスタブル耐火物である。比較例４は、ストロンチウムセメント量が本発明例より多い２１質量％であって、ＣａＯ含有量が本発明範囲より多いアルミナ－マグネシア－カーボンキャスタブル耐火物である。 Comparative Example 1 is an alumina-magnesia castable refractory using 7% by mass of alumina cement. Comparative Example 2 is an alumina-magnesia-carbon castable refractory using 7% by mass of alumina cement. Comparative Example 3 is an alumina-magnesia-carbon castable refractory using 6% by mass, which has a strontium cement amount smaller than the range of the present invention. Comparative Example 4 is an alumina-magnesia-carbon castable refractory having a strontium cement content of 21% by mass higher than that of the present invention and a CaO content higher than that of the present invention.
各原料を表１に従い、鱗状黒鉛、ピッチ、カーボンブラックのみ別袋にして２．５ｋｇになるように秤量、配合した後、粉体、液体とも５℃になっている冷蔵庫で１晩保存した。翌日、冷蔵庫から取り出して、鱗状黒鉛、ピッチ、カーボンブラック以外の原料を万能型ミキサーに入れ、１分間撹拌後に前記液体を入れ、２分間撹拌後、鱗状黒鉛、ピッチ、カーボンブラックを入れてさらに１分間撹拌した。その後、４０×４０×１６０ｍｍの金型に流し込み、テーブル状バイブレーターで３０秒加振した後、５℃になっている冷蔵庫に保管した。１日後に冷蔵庫から取り出し、脱型してＪＩＳ Ｒ ２５５３に従い、万能試験機を用いて曲げ試験を行った。曲げ試験の結果が０．８ＭＰａ以上あれば、冬季でも翌日に脱枠可能と判断する。 According to Table 1, each raw material was weighed and blended in a separate bag containing only scale graphite, pitch, and carbon black so as to weigh 2.5 kg, and then stored overnight in a refrigerator at 5 ° C. for both powder and liquid. The next day, take it out of the refrigerator, put raw materials other than scaly graphite, pitch, and carbon black in a universal mixer, add the liquid after stirring for 1 minute, and after stirring for 2 minutes, add scaly graphite, pitch, and carbon black, and add 1 more. Stir for minutes. Then, it was poured into a mold of 40 × 40 × 160 mm, vibrated with a table-shaped vibrator for 30 seconds, and then stored in a refrigerator at 5 ° C. One day later, it was taken out of the refrigerator, demolded, and subjected to a bending test using a universal testing machine according to JIS R 2553. If the result of the bending test is 0.8 MPa or more, it is judged that the frame can be removed the next day even in winter.
別途、各原料を表１に従い、鱗状黒鉛、ピッチ、カーボンブラックのみ別袋にして２．５ｋｇになるように秤量、配合した後、鱗状黒鉛、ピッチ、カーボンブラック以外の原料を万能型ミキサーに入れて１分間撹拌し、液体を入れて２分間撹拌後、鱗状黒鉛、ピッチ、カーボンブラックを入れてさらに１分間撹拌した。熱間曲げ試験用は３０×３０×１２０ｍｍの金型に流し込み、スラグ侵食試験用は４０×４０×４０ｍｍの金型に流し込んだ。型枠に流し込んだ後はテーブル状バイブレーターで３０秒加振した。２０℃で1日養生後に脱型した。 Separately, according to Table 1, weigh and mix each raw material into a separate bag containing only scale graphite, pitch, and carbon black so that the weight is 2.5 kg, and then put the raw materials other than scale graphite, pitch, and carbon black into a universal mixer. The mixture was stirred for 1 minute, liquid was added and stirred for 2 minutes, then scaly graphite, pitch and carbon black were added and stirred for another 1 minute. For the hot bending test, it was poured into a mold of 30 × 30 × 120 mm, and for the slag erosion test, it was poured into a mold of 40 × 40 × 40 mm. After pouring into the mold, it was vibrated for 30 seconds with a table-shaped vibrator. After curing at 20 ° C for 1 day, the mold was removed.
３０×３０×１２０ｍｍのサンプルは、１１０℃×２４時間乾燥した後、比較例１以外のサンプルは炭化珪素製の容器にコークスブリーズと共に入れて、比較例１のサンプルは容器に入れずに１４００℃×３時間電気炉で熱処理を行い、１４００℃に制御された電気炉内にコークスブリーズと共に入れてクロスヘッド下降速度０．５ｍｍ／分で熱間曲げ試験を行った。 The 30 × 30 × 120 mm sample was dried at 110 ° C. × 24 hours, and then the samples other than Comparative Example 1 were placed in a silicon carbide container together with coke breeze, and the sample of Comparative Example 1 was placed at 1400 ° C. without a container. Heat treatment was performed in an electric furnace for × 3 hours, and the mixture was placed in an electric furnace controlled at 1400 ° C. together with coke breeze to perform a hot bending test at a crosshead descent speed of 0.5 mm / min.
４０×４０×４０ｍｍのサンプルは、１１０℃×２４時間乾燥した後、１６５０℃×１時間、電気炉で窒素ガスを流しながら熱処理を行った。サンプル上部にφ２０×１５ｍｍ穴をあけ、その穴の中にＦｅ２Ｏ３＝０．９質量％、ＳｉＯ２＝５．０質量％、Ａｌ２Ｏ３＝１３．２質量％、ＣａＣＯ３＝７７．２質量％、ＭｇＯ＝３．８質量％に調整した試薬を７ｇ詰めて、再度１６５０℃×１時間、電気炉で窒素ガスを流しながら熱処理を行った。冷却後に試験前後の穴の直径の寸法変化を測定し、溶損厚みを求め、比較例１を１００として規格化し、溶損指数とした。結果を以下の表１に示す。 The 40 × 40 × 40 mm sample was dried at 110 ° C. × 24 hours and then heat-treated at 1650 ° C. × 1 hour while flowing nitrogen gas in an electric furnace. A hole of φ20 × 15 mm is made in the upper part of the sample, and Fe 2 O 3 = 0.9 mass%, SiO 2 = 5.0 mass%, Al 2 O 3 = 13.2 mass%, CaCO 3 = 77 in the hole. 7 g of the reagent adjusted to .2% by mass and MgO = 3.8% by mass was packed, and heat treatment was performed again at 1650 ° C. for 1 hour while flowing nitrogen gas in an electric furnace. After cooling, the dimensional change in the diameter of the hole before and after the test was measured to determine the melting loss thickness, and Comparative Example 1 was standardized as 100 and used as the melting loss index. The results are shown in Table 1 below.
表１の結果から以下のことがわかる。本発明例１～７は、いずれも５℃×１日養生後の曲げ強度が０．８ＭＰａ以上となり、ストロンチウムセメントを１１質量％以上使用した本発明例２～４は、アルミナセメントを７質量％使用した比較例１および２より高強度となった。ストロンチウムセメントを６質量％使用した比較例３は、５℃×１日養生後の曲げ強度が０．８ＭＰａ未満となった。 The following can be seen from the results in Table 1. In Examples 1 to 7 of the present invention, the bending strength after curing at 5 ° C. × 1 day is 0.8 MPa or more, and in Examples 2 to 4 of the present invention using 11% by mass or more of strontium cement, 7% by mass of alumina cement is used. The strength was higher than that of Comparative Examples 1 and 2 used. In Comparative Example 3 in which 6% by mass of strontium cement was used, the bending strength after curing at 5 ° C. for 1 day was less than 0.8 MPa.
鱗状黒鉛５質量％、アルミナセメント７質量％を使用した比較例２は、１４００℃×３時間熱処理後に膨張して亀裂が発生し、熱処理後の特性を評価することが出来なかったが、本発明例１～７は、いずれもアルミナセメント７質量％を使用した比較例１より１４００℃×３時間熱処理後の線変化率が小さくなった。 In Comparative Example 2 using 5% by mass of scaly graphite and 7% by mass of alumina cement, it expanded and cracked after heat treatment at 1400 ° C. for 3 hours, and the characteristics after heat treatment could not be evaluated. In each of Examples 1 to 7, the rate of linear change after heat treatment at 1400 ° C. for 3 hours was smaller than that in Comparative Example 1 in which 7% by mass of alumina cement was used.
本発明例１～７は、いずれもアルミナセメント７質量％を使用した比較例１と比べて１４００℃熱間曲げ強度が大きくなった。また、ＣａＯ分が少ないため、溶損指数が比較例１と比べて同等以下となり、耐食性が同等以上となった。 In each of Examples 1 to 7 of the present invention, the hot bending strength at 1400 ° C. was higher than that in Comparative Example 1 in which 7% by mass of alumina cement was used. Further, since the CaO content was small, the dissolution loss index was equal to or less than that of Comparative Example 1, and the corrosion resistance was equal to or higher than that of Comparative Example 1.
ストロンチウムセメント量が本発明例より多く、ＣａＯ分が多い比較例４では、ＣａＯの多さと施工に必要な水量が８．８質量％と多いため、溶損指数が比較例１より大きくなり、耐食性が劣った。 In Comparative Example 4 in which the amount of strontium cement is larger than that of the example of the present invention and the amount of CaO is large, the amount of CaO is large and the amount of water required for construction is as large as 8.8% by mass. Was inferior.
＜実施例２＞
以下の表２に、アルミナ－スピネル－カーボンキャスタブル耐火物に、ストロンチウムセメントを適用した本発明例１１～１７と比較例１３、１４、および、アルミナセメントを適用した比較例１２、さらに、アルミナ－スピネルキャスタブル耐火物に、アルミナセメントを適用した比較例１１を示す。
<Example 2>
Table 2 below shows Examples 11 to 17 of the present invention in which strontium cement was applied to an alumina-spinel-carbon castable refractory, Comparative Examples 13 and 14, and Comparative Example 12 in which alumina cement was applied, and further, alumina-spinel. Comparative Example 11 in which alumina cement is applied to a castable refractory is shown.
本発明例１１～１４は、いずれも鱗状黒鉛３質量％の場合であって、本発明例１１はストロンチウムセメント７質量％、本発明例１２はストロンチウムセメント１１質量％、本発明例１３はストロンチウムセメント１４質量％、本発明例１４はストロンチウムセメント２０質量％を使用したアルミナ－スピネル－カーボンキャスタブル耐火物である。本発明例１５～１７は、いずれもストロンチウムセメント７質量％の場合であって、本発明例１５は鱗状黒鉛１質量％、本発明例１６は鱗状黒鉛１０質量％、本発明例１７はピッチ１．５質量％とカーボンブラック１．５質量％を使用したアルミナ－スピネル－カーボンキャスタブル耐火物である。 Examples 11 to 14 of the present invention are all cases of scale graphite 3% by mass, Example 11 of the present invention is 7% by mass of strontium cement, Example 12 of the present invention is 11% by mass of strontium cement, and Example 13 of the present invention is strontium cement. 14% by mass, Example 14 of the present invention is an alumina-spinel-carbon castable refractory using 20% by mass of strontium cement. Examples 15 to 17 of the present invention are all cases of 7% by mass of strontium cement, Example 15 of the present invention is 1% by mass of scaly graphite, Example 16 of the present invention is 10% by mass of scaly graphite, and Example 17 of the present invention is pitch 1. Alumina-spinel-carbon castable fireproof material using 5.5% by mass and 1.5% by mass of carbon black.
比較例１１は、アルミナセメント７質量％を使用したアルミナ－スピネルキャスタブル耐火物である。比較例１２は、アルミナセメント７質量％を使用したアルミナ－スピネル－カーボンキャスタブル耐火物である。比較例１３は、ストロンチウムセメント量が本発明範囲より少ない６質量％を使用したアルミナ－スピネル－カーボンキャスタブル耐火物である。比較例１４は、ストロンチウムセメント量が本発明例より多い２１質量％であって、ＣａＯ分が本発明範囲より多いアルミナ－スピネル－カーボンキャスタブル耐火物である。 Comparative Example 11 is an alumina-spinel castable refractory using 7% by mass of alumina cement. Comparative Example 12 is an alumina-spinel-carbon castable refractory using 7% by mass of alumina cement. Comparative Example 13 is an alumina-spinel-carbon castable refractory using 6% by mass, which has a strontium cement amount smaller than the range of the present invention. Comparative Example 14 is an alumina-spinel-carbon castable refractory in which the amount of strontium cement is 21% by mass, which is larger than that of the present invention, and the CaO content is larger than the range of the present invention.
各原料を使用して、実施例１と同様にサンプルを作製し、作製したサンプルを評価した。結果を以下の表２に示す。 Using each raw material, a sample was prepared in the same manner as in Example 1, and the prepared sample was evaluated. The results are shown in Table 2 below.
表２の結果から以下のことがわかる。本発明例１１～１７は、いずれも５℃×１日養生後の曲げ強度が０．８ＭＰａ以上となり、ストロンチウムセメントを１１質量％以上使用した本発明例１２～１４は、アルミナセメント７質量％を使用した比較例１１および１２より高強度となった。ストロンチウムセメントを６質量％使用した比較例１２は、５℃×１日養生後の曲げ強度が０．８ＭＰａ未満となった。 The following can be seen from the results in Table 2. In the examples 11 to 17 of the present invention, the bending strength after curing at 5 ° C. × 1 day is 0.8 MPa or more, and in the examples 12 to 14 of the present invention using 11% by mass or more of strontium cement, 7% by mass of alumina cement is used. The strength was higher than that of Comparative Examples 11 and 12 used. In Comparative Example 12 in which 6% by mass of strontium cement was used, the bending strength after curing at 5 ° C. for 1 day was less than 0.8 MPa.
鱗状黒鉛３質量％、アルミナセメント７質量％を含有する比較例１２は、１４００℃×３時間熱処理後に膨張し、施工体に亀裂が発生したが、本発明例１１～１７は、いずれもアルミナセメント７質量％を含有する比較例１１と同等の線変化率となり、亀裂は発生しなかった。 Comparative Example 12 containing 3% by mass of scaly graphite and 7% by mass of alumina cement expanded after heat treatment at 1400 ° C. for 3 hours, and cracks were generated in the construction body. However, all of Examples 11 to 17 of the present invention were alumina cement. The linear change rate was the same as that of Comparative Example 11 containing 7% by mass, and no crack was generated.
本発明例１１～１７は、いずれもアルミナセメント７質量％を使用した比較例１１と比べて１４００℃熱間曲げ強度が大きくなった。また、ＣａＯ分が少ないため溶損指数が比較例１１と比べて同等以下となり、耐食性が同等以上であった。 In each of Examples 11 to 17 of the present invention, the hot bending strength at 1400 ° C. was higher than that in Comparative Example 11 in which 7% by mass of alumina cement was used. Further, since the CaO content was small, the dissolution loss index was equal to or less than that of Comparative Example 11, and the corrosion resistance was equal to or higher than that of Comparative Example 11.
ストロンチウムセメント量が本発明例より多く、ＣａＯ分が多い比較例１４では、ＣａＯの多さと施工に必要な水量が８．５質量％と多いため、溶損指数が比較例１１より大きくなり、耐食性が劣った。 In Comparative Example 14 in which the amount of strontium cement is larger than that of the example of the present invention and the amount of CaO is large, the amount of CaO is large and the amount of water required for construction is as large as 8.5% by mass. Was inferior.
＜実施例３＞
本発明例１２のアルミナ－スピネル－カーボンキャスタブル耐火物を、容量３００ｔの溶鋼鍋の敷部に１１．５ｔを流し込み施工した。また、比較例１のアルミナ－マグネシアキャスタブル耐火物を、別の３００ｔ溶鋼鍋の敷部に１２ｔ流し込み施工した。いずれも1日後に鋼浴部にアルミナ－マグネシアキャスタブル耐火物を流し込み、スラグライン部にマグネシア－カーボンれんがを積んだ。その後、どちらの溶鋼鍋も同じ条件で乾燥・予熱して溶鋼を受鋼した。本発明例１２の方が施工量が少ないのは、黒鉛のかさ比重がアルミナより小さいことから、アルミナ－スピネル－カーボンキャスタブル耐火物の方がアルミナ－マグネシアキャスタブル耐火物よりかさ比重が小さくなるためである。比較例１では１１０回使用後に補修を行ったのに対し、本発明例では１３２回使用することが出来た。
<Example 3>
The alumina-spinel-carbon castable refractory of Example 12 of the present invention was constructed by pouring 11.5 tons into the base of a molten steel pot having a capacity of 300 tons. Further, the alumina-magnesia castable refractory of Comparative Example 1 was cast by pouring 12 tons into the floor of another 300 ton molten steel pot. In each case, one day later, alumina-magnesia castable refractory was poured into the steel bath part, and magnesia-carbon brick was loaded on the slag line part. After that, both molten steel pots were dried and preheated under the same conditions to receive the molten steel. The reason why the construction amount of Example 12 of the present invention is smaller is that the bulk specific gravity of graphite is smaller than that of alumina, and therefore the bulk specific gravity of the alumina-spinel-carbon castable refractory is smaller than that of the alumina-magnesia castable refractory. be. In Comparative Example 1, the repair was performed after 110 times of use, whereas in the example of the present invention, it could be used 132 times.
上述した実施例から明らかなように、本発明に係るキャスタブル耐火物は、高い熱間強度と優れた耐食性を得ることができ、施工体に亀裂が生じにくい。そのため、本発明に係るキャスタブル耐火物を内張耐火物として用いた溶鋼鍋は、高熱の下で使用されても高い耐用性を有する。 As is clear from the above-mentioned examples, the castable refractory material according to the present invention can obtain high hot strength and excellent corrosion resistance, and cracks are less likely to occur in the construction body. Therefore, the molten steel pot using the castable refractory according to the present invention as the lining refractory has high durability even when used under high heat.
本発明に係るキャスタブル耐火物は、上記の実施例に限定されるものではなく、本発明の範囲において種々の応用を加えることが可能であり、製鉄所内で使用されるキャスタブル耐火物全てにおいて応用が可能である。 The castable refractory material according to the present invention is not limited to the above embodiment, and various applications can be added within the scope of the present invention, and the castable refractory material used in the steelworks can be applied to all castable refractory materials. It is possible.
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| JP2016145117A (en) * | 2015-02-06 | 2016-08-12 | 新日鐵住金株式会社 | Heat insulating monolithic refractory |
| JP2017066025A (en) * | 2015-09-29 | 2017-04-06 | 新日鐵住金株式会社 | Monolithic refractory |
| WO2019049992A1 (en) * | 2017-09-11 | 2019-03-14 | 黒崎播磨株式会社 | Monolithic refractory |
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| JPS56104782A (en) * | 1980-01-24 | 1981-08-20 | Asahi Glass Co Ltd | Heat resistant castable blend |
| JPS56104783A (en) * | 1980-01-24 | 1981-08-20 | Asahi Glass Co Ltd | Castable blend |
| JPH0450178A (en) * | 1990-06-15 | 1992-02-19 | Kurosaki Refract Co Ltd | Ladle-lining carbon-containing amorphous refractories |
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| JP2004307277A (en) * | 2003-04-08 | 2004-11-04 | Mino Ceramic Co Ltd | Castable molded article and method of manufacturing the same |
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| JP2016145117A (en) * | 2015-02-06 | 2016-08-12 | 新日鐵住金株式会社 | Heat insulating monolithic refractory |
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| WO2019049992A1 (en) * | 2017-09-11 | 2019-03-14 | 黒崎播磨株式会社 | Monolithic refractory |
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