JP5995315B2 - Irregular refractory - Google Patents
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- JP5995315B2 JP5995315B2 JP2012194237A JP2012194237A JP5995315B2 JP 5995315 B2 JP5995315 B2 JP 5995315B2 JP 2012194237 A JP2012194237 A JP 2012194237A JP 2012194237 A JP2012194237 A JP 2012194237A JP 5995315 B2 JP5995315 B2 JP 5995315B2
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- 230000001788 irregular Effects 0.000 title description 7
- 239000011029 spinel Substances 0.000 claims description 121
- 229910052596 spinel Inorganic materials 0.000 claims description 121
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 100
- 239000002994 raw material Substances 0.000 claims description 84
- 239000004568 cement Substances 0.000 claims description 71
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 57
- 239000000395 magnesium oxide Substances 0.000 claims description 39
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 44
- 239000002893 slag Substances 0.000 description 41
- 239000011819 refractory material Substances 0.000 description 35
- 230000008595 infiltration Effects 0.000 description 31
- 238000001764 infiltration Methods 0.000 description 31
- 230000007797 corrosion Effects 0.000 description 30
- 238000005260 corrosion Methods 0.000 description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000004901 spalling Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 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 7
- 230000003628 erosive effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000029087 digestion Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 235000013312 flour Nutrition 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000009628 steelmaking Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000011823 monolithic refractory Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- -1 calcium aluminates Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Description
本発明は、主に製鋼処理装置に使用される不定形耐火物に関する。 The present invention relates to an irregular refractory mainly used in a steelmaking processing apparatus.
製鋼処理装置においては、溶鋼やスラグと接触する耐火物として、非特許文献１及び２に示されるようなアルミナ−スピネル質、アルミナ−マグネシア質、アルミナ−スピネル−マグネシア質の不定形耐火物が使用されている。なお、本明細書において、スピネルとは、ＭｇＯ−Ａｌ２Ｏ３系の化合物で、化学組成がＭｇＯ・Ａｌ２Ｏ３の化学量論組成及びＭｇＯあるいはＡｌ２Ｏ３が過剰に固溶した非化学量論組成の化合物のことをいう。 In steelmaking processing equipment, as refractories that come into contact with molten steel or slag, the amorphous refractories of alumina-spinel, alumina-magnesia, alumina-spinel-magnesia as shown in Non-Patent Documents 1 and 2 are used. Has been. In the present specification, spinel is an MgO—Al 2 O 3 based compound, the chemical composition of which is a stoichiometric composition of MgO · Al 2 O 3 , and a non-solid solution in which MgO or Al 2 O 3 is excessively dissolved. A compound having a stoichiometric composition.
アルミナ−スピネル質の不定形耐火物は、スピネルがＦｅＯを固溶するので酸素洗浄や製鋼用スラグに対する耐食性と耐スラグ浸潤性が高く、更に、熱間強度が大きく、受熱後の残存膨張収縮が小さく体積安定性が高い特徴を有している。 Alumina-spinel amorphous refractories have high corrosion resistance and slag infiltration resistance against oxygen scrubbing and steelmaking slag because spinel dissolves in FeO, and also has high hot strength and residual expansion and shrinkage after receiving heat. It has small and high volume stability.
アルミナ−マグネシア質の不定形耐火物は、使用中に１１００〜１２００℃以上に加熱されると材料中のアルミナとマグネシアが反応して微細なスピネルが形成され、この微細なスピネルが高い耐食性と耐スラグ浸潤性を示す。スピネルが微細な方が耐食性と耐スラグ浸潤性が高いので、一般的にアルミナ−マグネシア質の不定形耐火物は、アルミナ−スピネル質の不定形耐火物よりも耐食性と耐スラグ浸潤性が良好である。しかし、微細なスピネルを形成する反応が体積膨張を伴い、加熱された稼働面側だけでスピネル生成による膨張が発生するので稼働面側に大きな剥離や亀裂が発生する欠点があり、アルミナ−マグネシア質の不定形耐火物は、一般的に耐熱スポーリング性はアルミナ−スピネル質の不定形耐火物に劣る。 When the alumina-magnesia amorphous refractory is heated to 1100-1200 ° C. or more during use, the alumina and magnesia in the material react to form fine spinel, and this fine spinel has high corrosion resistance and resistance. Shows slag infiltration. Since finer spinel has higher corrosion resistance and slag infiltration, alumina-magnesia amorphous refractories generally have better corrosion resistance and slag infiltration than alumina-spinel amorphous refractories. is there. However, the reaction to form fine spinel involves volume expansion, and expansion due to spinel generation occurs only on the heated working surface side, so there is a drawback that large peeling or cracking occurs on the working surface side, and the alumina-magnesia In general, the amorphous refractories are inferior to the alumina-spinel refractories in heat spalling properties.
アルミナ−スピネル−マグネシア質の不定形耐火物は、アルミナ−スピネル質とアルミナ−マグネシア質の不定形耐火物の両方の特徴を有しており、体積安定性、耐食性、耐スラグ浸潤性は両不定形耐火物の中間の特性を示す。 Alumina-spinel-magnesia amorphous refractories have characteristics of both alumina-spinel and alumina-magnesia amorphous refractories, and volume stability, corrosion resistance, and slag infiltration resistance are both inferior. Shows intermediate properties of regular refractories.
特許文献１は、粒径が５μｍ以下の微細なスピネルを使用したアルミナ−スピネル質の不定形耐火物を示しており、アルミナ−マグネシア質の不定形耐火物において使用中に形成される微細なスピネルを最初から含有させることで、アルミナ−スピネル質の不定形耐火物の耐食性と耐スラグ浸潤性を高めている。 Patent Document 1 shows an alumina-spinel amorphous refractory using a fine spinel having a particle size of 5 μm or less, and the fine spinel formed during use in an alumina-magnesia amorphous refractory. From the beginning, the corrosion resistance and slag infiltration resistance of the alumina-spinel amorphous refractories are enhanced.
また、非特許文献１、２及び特許文献２は、スピネルを含有したアルミナセメント（本明細書では「スピネル含有アルミナセメント」という。）を使用したアルミナ−スピネル質とアルミナ−スピネル−マグネシア質の不定形耐火物を示している。 Non-Patent Documents 1 and 2 and Patent Document 2 describe the non-alumina-spinel and alumina-spinel-magnesia quality using spinel-containing alumina cement (referred to herein as “spinel-containing alumina cement”). Shows regular refractories.
一般のアルミナセメントは、ＣａＯ・Ａｌ２Ｏ３、ＣａＯ・２Ａｌ２Ｏ３を主な成分とし、一部のアルミナセメントは１２ＣａＯ・７Ａｌ２Ｏ３やＡｌ２Ｏ３等も含有しており、ＣａＯ・Ａｌ２Ｏ３、ＣａＯ・２Ａｌ２Ｏ３及び１２ＣａＯ・７Ａｌ２Ｏ３が水硬性を示すので、不定形耐火物の結合材として使用されている。 General alumina cement contains CaO · Al 2 O 3 and CaO · 2Al 2 O 3 as main components, and some alumina cements contain 12CaO · 7Al 2 O 3 and Al 2 O 3 as well. · Al 2 O 3, CaO · 2Al 2 O 3 and 12CaO · 7Al 2 O 3 is exhibits a hydraulic, is used as a binder for monolithic refractories.
また、一般のアルミナセメントを使用したアルミナ−スピネル質とアルミナ−スピネル−マグネシア質の不定形耐火物は、使用中の稼働面近くの相が主にＡｌ２Ｏ３、スピネル及びＣａＯ・６Ａｌ２Ｏ３になっており、骨材のＡｌ２Ｏ３を除くマトリックス部と称されている部分は、主にスピネルとＣａＯ・６Ａｌ２Ｏ３から形成され、この２つの相が細かく均一に分散していると高い耐食性と耐スラグ浸潤性を示す。 Also, the amorphous refractories of alumina-spinel and alumina-spinel-magnesia using general alumina cement are mainly composed of Al 2 O 3 , spinel and CaO.6Al 2 O in the phase near the operating surface during use. The portion of the aggregate called the matrix portion excluding Al 2 O 3 is mainly formed of spinel and CaO · 6Al 2 O 3 , and these two phases are finely and uniformly dispersed. When it is, it shows high corrosion resistance and slag infiltration resistance.
非特許文献１、２に示されているスピネル含有アルミナセメントは、微細なスピネルとＣａＯ・Ａｌ２Ｏ３及びＣａＯ・２Ａｌ２Ｏ３が均一に分散したものであり、このスピネル含有アルミナセメントを使用したアルミナ−スピネル質とアルミナ−スピネル−マグネシア質の不定形耐火物は、マトリックス部に微細で均一に分散したスピネルとＣａＯ・６Ａｌ２Ｏ３が形成されるので高い耐食性と耐スラグ浸潤性を示す。 Spinel containing alumina cement disclosed in Non-Patent Documents 1 and 2, which have fine spinel and CaO · Al 2 O 3 and CaO · 2Al 2 O 3 was uniformly dispersed, using the spinel-containing alumina cement Alumina-spinel and alumina-spinel-magnesia amorphous refractories show high corrosion resistance and slag infiltration because fine and uniformly dispersed spinel and CaO.6Al 2 O 3 are formed in the matrix part. .
上記特許文献１に示されているような超微粉スピネルを使用したアルミナ-スピネル質の不定形耐火物、上記非特許文献１、２に示されているようなスピネル含有アルミナセメントを使用したアルミナ−スピネル質及びアルミナ−スピネル−マグネシア質の不定形耐火物は、耐食性と耐スラグ浸潤性が高められてはいるが、製鋼プロセスは苛酷であり、また、コスト削減のために更なる耐用の改善が求められている。 Alumina using spinel-like amorphous refractories using ultrafine spinel as shown in Patent Document 1 above, Alumina using spinel-containing alumina cement as shown in Non-Patent Documents 1 and 2 above Spinel and alumina-spinel-magnesia amorphous refractories have enhanced corrosion resistance and slag infiltration, but the steelmaking process is harsh, and further durability improvements are needed to reduce costs. It has been demanded.
また、超微粉スピネルを使用したアルミナ−スピネル質の不定形耐火物は、所望の特性を得るためには超微粉スピネルとアルミナセメントが均一に混合分散するように、強力な混和装置や混練ミキサーを使用しなければならない。 In addition, alumina-spinel-shaped amorphous refractories using ultrafine spinel must be equipped with a powerful mixing device or kneading mixer so that ultrafine spinel and alumina cement are uniformly mixed and dispersed in order to obtain the desired characteristics. Must be used.
一方、スピネル含有アルミナセメントを使用したアルミナ−スピネル質及びアルミナ−スピネル−マグネシア質の不定形耐火物は、マトリックス部に微細で均一に分散したスピネルとＣａＯ・６Ａｌ２Ｏ３を容易に形成することが可能であるが、微細で均一に分散するために焼結しやすく、熱スポーリングによる亀裂剥離が発生しやすくなる。 On the other hand, alumina-spinel and alumina-spinel-magnesia refractories using spinel-containing alumina cement can easily form fine and evenly dispersed spinel and CaO.6Al 2 O 3 in the matrix part. However, since it is finely and uniformly dispersed, it is easy to sinter, and crack peeling due to thermal spalling is likely to occur.
そこで、本発明が解決しようとする課題は、スピネル含有アルミナセメントを使用した不定形耐火物の耐食性と耐スラグ浸潤性を更に高めるとともに、亀裂剥離の発生を低減することにある。 Therefore, the problem to be solved by the present invention is to further improve the corrosion resistance and slag infiltration resistance of the amorphous refractory using the spinel-containing alumina cement and reduce the occurrence of crack peeling.
かかる課題を解決するため、本発明の要旨とするところは、
（１）アルミナセメントとして少なくともスピネル含有アルミナセメントを含む粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、アルミナセメントに含まれるＣａＯ量が０．５〜２．５質量％、スピネル含有アルミナセメントに含まれるスピネル量が３．５〜１０．５質量％、スピネル含有アルミナセメントに含まれるスピネルと粒径０．１ｍｍ以下のスピネル原料との合計量が５．５〜２２質量％である不定形耐火物、
（２）アルミナセメントとして少なくともスピネル含有アルミナセメントを含む粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、アルミナセメントに含まれるＣａＯ量が０．５〜２．５質量％、スピネル含有アルミナセメントに含まれるスピネル量が３．５〜１０．５質量％、粒径０．１ｍｍ以下のマグネシア原料の含有量が３〜９質量％である不定形耐火物、
（３）前記耐火原料１００質量％に占める割合で、粒径が３μｍ以下の仮焼アルミナの含有量が４〜１０質量％である（１）又は（２）に記載の不定形耐火物、
（４）前記耐火原料が、粒径が０．１ｍｍ超８ｍｍ以下のアルミナ原料及びスピネル原料の少なくとも１種を合計で５０〜７５質量％含有する（１）〜（３）のいずれかに記載の不定形耐火物、
にある。
In order to solve this problem, the gist of the present invention is as follows:
(1) As a proportion of 100% by mass of refractory raw material having a particle size of 8 mm or less and containing at least spinel-containing alumina cement as alumina cement, the amount of CaO contained in alumina cement is 0.5 to 2.5% by mass, and spinel-containing alumina The amount of spinel contained in the cement is 3.5 to 10.5% by mass, and the total amount of the spinel contained in the spinel-containing alumina cement and the spinel raw material having a particle size of 0.1 mm or less is 5.5 to 22% by mass. Shaped refractories,
( 2 ) The proportion of the refractory raw material containing at least spinel-containing alumina cement as an alumina cement to 100 mass% of the particle size of 8 mm or less, the amount of CaO contained in the alumina cement is 0.5 to 2.5 mass%, spinel-containing alumina The amount of spinel contained in the cement is 3.5 to 10.5% by mass , and the content of the magnesia raw material having a particle size of 0.1 mm or less is 3 to 9% by mass .
( 3 ) The amorphous refractory according to (1) or (2) , wherein the content of calcined alumina having a particle size of 3 μm or less is 4 to 10% by mass in a proportion of 100% by mass of the refractory raw material,
( 4 ) The refractory raw material according to any one of (1) to (3) , containing a total of 50 to 75% by mass of an alumina raw material and a spinel raw material having a particle size of more than 0.1 mm and not more than 8 mm. Irregular refractories,
It is in.
本発明によれば、スピネル含有アルミナセメントから不定形耐火物に配合されるスピネル量とＣａＯ量を最適化することによって、その不定形耐火物の耐食性、耐スラグ浸潤性を高めることができ、更に熱スポーリングによる亀裂剥離の発生を少なくすることができる。 According to the present invention, by optimizing the amount of spinel and CaO blended into the amorphous refractory from the spinel-containing alumina cement, the corrosion resistance of the amorphous refractory and the slag infiltration resistance can be improved. The occurrence of crack peeling due to thermal spalling can be reduced.
本発明は、主に、アルミナ−スピネル質不定形耐火物とアルミナ−スピネル−マグネシア質不定形耐火物に適用することができる。 The present invention is mainly applicable to alumina-spinel amorphous refractories and alumina-spinel-magnesia amorphous refractories.
本発明によるアルミナ−スピネル質不定形耐火物は、主に、スピネル含有アルミナセメント、アルミナ原料、スピネル原料、及び通常の不定形耐火物に使用される混和材と混和剤によって構成される。また、本発明によるアルミナ−スピネル−マグネシア質不定形耐火物は、主に、スピネル含有アルミナセメント、アルミナ原料、スピネル原料、マグネシア原料、シリカフラワー、及び通常の不定形耐火物に使用される混和材と混和剤によって構成される。ただし、乾燥時のマグネシアの消化に問題がない場合、熱間強度が重視される場合等は、シリカフラワーを使用しないことがある。 The alumina-spinel amorphous refractories according to the present invention are mainly composed of admixtures and admixtures used for spinel-containing alumina cement, alumina raw materials, spinel raw materials, and ordinary amorphous refractories. Further, the alumina-spinel-magnesia amorphous refractory according to the present invention is mainly composed of spinel-containing alumina cement, alumina raw material, spinel raw material, magnesia raw material, silica flour, and admixture used for ordinary amorphous refractories. And composed of admixtures. However, silica flour may not be used when there is no problem in digestion of magnesia during drying, or when hot strength is important.
本発明においては、上記混和材を除く耐火原料全体を耐火原料という。本発明では混和剤を耐火原料に含めるが、これは不定形耐火物として全原料を混和した後に分離が困難だからである。 In the present invention, the entire refractory raw material excluding the admixture is called a refractory raw material. In the present invention, the admixture is included in the refractory raw material because separation is difficult after all raw materials are mixed as an amorphous refractory.
なお、混和材は、通常の不定形耐火物で使用されている有機繊維、Ａｌ粉末、メタルファイバー等、混和剤は、通常の不定形耐火物で使用されている減水剤、ＡＥ剤、消泡剤、硬化調整剤、流動性調整剤、マグネシアの消化防止剤、爆裂防止剤等をいう。 In addition, admixtures are organic fibers, Al powder, metal fibers, etc. used in ordinary amorphous refractories, and admixtures are water reducing agents, AE agents, antifoams used in ordinary irregular refractories. Agents, curing modifiers, fluidity modifiers, magnesia digestion inhibitors, explosion inhibitors, and the like.
スピネル含有アルミナセメントとは、Ｋｅｒｎｅｏｓ社から発売されているＣＭＡ７２のように、主に微細なスピネルと水硬性を示すＣａＯ・Ａｌ２Ｏ３、ＣａＯ・２Ａｌ２Ｏ３の混合物からなるセメントのことであるが、１２ＣａＯ・７Ａｌ２Ｏ３等のその他のアルミン酸カルシウム、Ａｌ２Ｏ３を含んでいても良い。また、ＳｉＯ２やＦｅ２Ｏ３等の不純物に由来する成分、非晶質相、減水剤、硬化調整のための混和剤等を含んでいても良い。 The spinel-containing alumina cement is a cement composed mainly of a mixture of fine spinel and CaO · Al 2 O 3 and CaO · 2Al 2 O 3 exhibiting hydraulic properties, such as CMA72 sold by Kerneos. However, other calcium aluminates such as 12CaO · 7Al 2 O 3 and Al 2 O 3 may also be included. Further, components derived from impurities such as SiO 2 and Fe 2 O 3, amorphous phase, water reducing agent, may contain admixtures like for curing adjustment.
また、本発明の不定形耐火物においては、必要に応じてスピネル含有アルミナセメントに加えてアルミナセメントを使用することができ、本発明では、アルミナセメントとして少なくともスピネル含有アルミナセメントを含む粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、アルミナセメント（スピネル含有アルミナセメント及びそれ以外のアルミナセメントの合計部）に含まれるＣａＯ量が０．５〜２．５質量％となるようにする。これらのスピネル含有アルミナセメント及びそれ以外のアルミナセメントは、いずれも大部分が粒径０．１ｍｍ以下であり、不定形耐火物のマトリックス部を構成する。 In addition, in the amorphous refractory according to the present invention, an alumina cement can be used in addition to the spinel-containing alumina cement as necessary. In the present invention, the particle size including at least the spinel-containing alumina cement as the alumina cement is 8 mm. The CaO amount contained in alumina cement (the total part of spinel-containing alumina cement and other alumina cements) is 0.5 to 2.5% by mass in the following proportion of 100% by mass of the refractory raw material. Most of these spinel-containing alumina cements and other alumina cements have a particle size of 0.1 mm or less, and constitute a matrix part of an amorphous refractory.
このように本発明では、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、ＣａＯ量や後述するスピネル量等を規定するが、これは、不定形耐火物の耐食性、耐スラグ浸潤性及び強度が、粒径が８ｍｍ以下の耐火原料の化学組成及びアルミナセメント量の影響を大きく受けるからである。 Thus, in the present invention, the proportion of CaO and the amount of spinel, which will be described later, are defined as a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less. This is the corrosion resistance and slag infiltration resistance of amorphous refractories. This is because the strength is greatly influenced by the chemical composition of the refractory raw material having a particle size of 8 mm or less and the amount of alumina cement.
アルミナ−スピネル質あるいはアルミナ−スピネル−マグネシア質の不定形耐火物の化学組成は，不純物成分を除くとＡｌ２Ｏ３−ＭｇＯ−ＣａＯ系あるいはＡｌ２Ｏ３−ＭｇＯ−ＣａＯ−ＳｉＯ２系であり、ＣａＯ含有量が少ないと製鋼用スラグに対する溶解量が少なく耐食性が高くなる。また、スラグ中のＣａＯは不定形耐火物中のＡｌ２Ｏ３と反応してＣａＯ・６Ａｌ２Ｏ３として捕捉され、浸潤するスラグは徐々にＣａＯ／ＳｉＯ２が小さくなって粘性が増加するので、不定形耐火物中のＣａＯ含有量が少ないと浸潤するスラグ先端のＣａＯ／ＳｉＯ２の低下による粘性の増加が早く、その結果としてスラグ浸潤が少なくなる。 The chemical composition of the amorphous refractory of alumina-spinel or alumina-spinel-magnesia is Al 2 O 3 —MgO—CaO or Al 2 O 3 —MgO—CaO—SiO 2 excluding impurity components. If the CaO content is small, the amount of dissolution with respect to the steelmaking slag is small and the corrosion resistance is high. In addition, CaO in the slag reacts with Al 2 O 3 in the amorphous refractory and is captured as CaO · 6Al 2 O 3 , and the infiltrating slag gradually decreases in CaO / SiO 2 and increases in viscosity. When the content of CaO in the amorphous refractory is small, the viscosity increases rapidly due to the decrease in CaO / SiO 2 at the infiltrating slag tip, resulting in less slag infiltration.
このようにＣａＯ量を少なくする、すなわちアルミナセメントの使用量を少なくすると耐食性と耐スラグ浸潤性が高くなることは、従来の不定形耐火物でも同様であるが、これまではアルミナセメント量を少なくすると強度が必要以上に低下する欠点があった。これに対して本発明の不定形耐火物は、そのマトリックス部に、スピネル含有アルミナセメントに由来するスピネル、ＣａＯ・Ａｌ２Ｏ３、ＣａＯ・２Ａｌ２Ｏ３が微細に均一に分散しているために焼結しやすく、ＣａＯ量すなわちアルミナセメントの使用量を少なくしても強度の低下が少ない。 As described above, when the amount of CaO is decreased, that is, when the amount of alumina cement used is decreased, the corrosion resistance and the slag infiltration resistance increase, as in the case of conventional amorphous refractories. Then, there existed a fault which intensity | strength fell more than needed. Monolithic refractory of the present invention contrast, in the matrix portion, a spinel derived from spinel containing alumina cement, since the CaO · Al 2 O 3, CaO · 2Al 2 O 3 are uniformly dispersed finely It is easy to sinter, and even if the amount of CaO, that is, the amount of alumina cement used is reduced, the decrease in strength is small.
ＣａＯ量を０．５〜２．５質量％とするのは、ＣａＯ量が０．５質量％より少なくなるセメント量では強度が低くなり過ぎ、ＣａＯ量が２．５質量％より多くなると耐食性と耐スラグ浸潤性の改善が得られないからである。本発明の不定形耐火物では、上述のとおりＣａＯ量すなわちアルミナセメントの使用量を少なくしても強度の低下は少ないが、ＣａＯ量が０．５質量％より少なくなると強度が低くなり過ぎる。 The reason why the CaO amount is 0.5 to 2.5% by mass is that the strength becomes too low at the cement amount where the CaO amount is less than 0.5% by mass, and the corrosion resistance is increased when the CaO amount exceeds 2.5% by mass. This is because improvement of slag infiltration resistance cannot be obtained. In the amorphous refractory according to the present invention, as described above, the decrease in strength is small even if the amount of CaO, that is, the amount of alumina cement used is reduced, but the strength becomes too low when the amount of CaO is less than 0.5% by mass.
本発明の不定形耐火物は、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、スピネル含有アルミナセメントに含まれるスピネル量が３．５〜１０．５質量％である。スピネル含有アルミナセメントに含まれるスピネルは、粒径が０．１ｍｍ以下の微細なスピネルであり、ＣａＯ・Ａｌ２Ｏ３、ＣａＯ・２Ａｌ２Ｏ３等と均一に分散しているが、このスピネル量が３．５質量％より少ないと、本発明の目的である耐食性と耐スラグ浸潤性の向上効果が得られない。また、スピネル含有アルミナセメントに含まれるスピネル量が１０．５質量％より多くなると、使用中に稼働面側の焼結が進んで亀裂剥離が多くなる。 The amorphous refractory according to the present invention is a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less, and the amount of spinel contained in the spinel-containing alumina cement is 3.5 to 10.5% by mass. Spinel included in the spinel-containing alumina cement has a particle size is less fine spinel 0.1mm, CaO · Al 2 O 3 , CaO · 2Al 2 O 3 or the like and are uniformly dispersed, this spinel weight If it is less than 3.5% by mass, the effect of improving the corrosion resistance and slag infiltration resistance, which is the object of the present invention, cannot be obtained. Further, if the amount of spinel contained in the spinel-containing alumina cement is more than 10.5% by mass, sintering on the working surface side proceeds during use and crack peeling increases.
本発明の不定形耐火物は、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、アルミナセメントに含まれるＣａＯ量が０．５〜２．５質量％、スピネル含有アルミナセメントに含まれるスピネル量が３．５〜１０．５質量％であり、更に、スピネル含有アルミナセメントに含まれるスピネルと粒径０．１ｍｍ以下のスピネル原料との合計量が５．５〜２２質量％であることが好ましい。このように調整すると、耐食性と耐スラグ浸潤性が高く、高強度で、かつ、耐熱スポーリング性が高い不定形耐火物を得ることができる。更に、０．１ｍｍより大きい粒径のスピネル原料を組み合わせて使用することで、耐食性と耐スラグ浸潤性を高めることも可能である。 The amorphous refractory according to the present invention is contained in the spinel-containing alumina cement in a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less, and the CaO amount contained in the alumina cement is 0.5 to 2.5% by mass. The spinel amount is 3.5 to 10.5% by mass, and the total amount of the spinel contained in the spinel-containing alumina cement and the spinel raw material having a particle size of 0.1 mm or less is 5.5 to 22% by mass. Is preferred. By adjusting in this way, an amorphous refractory having high corrosion resistance and slag infiltration resistance, high strength, and high heat spalling resistance can be obtained. Furthermore, it is also possible to improve corrosion resistance and slag infiltration resistance by using a combination of spinel raw materials having a particle size larger than 0.1 mm.
また、本発明の不定形耐火物は、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、アルミナセメントに含まれるＣａＯ量が０．５〜２．５質量％、スピネル含有アルミナセメントに含まれるスピネル量が３．５〜１０．５質量％であり、更に、粒径０．１ｍｍ以下のマグネシア原料の含有量が３〜９質量％であることが好ましい。このように調整すると、耐食性と耐スラグ浸潤性が高く、高強度で、かつ、耐熱スポーリング性が高い不定形耐火物を得ることができる。 In addition, the amorphous refractory of the present invention is a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less, and the amount of CaO contained in the alumina cement is 0.5 to 2.5% by mass. The amount of spinel contained is 3.5 to 10.5% by mass, and the content of magnesia raw material having a particle size of 0.1 mm or less is preferably 3 to 9% by mass. By adjusting in this way, an amorphous refractory having high corrosion resistance and slag infiltration resistance, high strength, and high heat spalling resistance can be obtained.
更に、本発明の不定形耐火物は、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、粒径が３μｍ以下の仮焼アルミナの含有量が４〜１０質量％であることが好ましい。このように調整すると、耐食性と耐スラグ浸潤性が高く、高強度で、かつ、耐熱スポーリング性が高い不定形耐火物を得ることができる。 Further, the amorphous refractory of the present invention is preferably a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less, and the content of calcined alumina having a particle size of 3 μm or less is 4 to 10% by mass. . By adjusting in this way, an amorphous refractory having high corrosion resistance and slag infiltration resistance, high strength, and high heat spalling resistance can be obtained.
ここで、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合としての、粒径が３μｍ以下の仮焼アルミナの含有量は、次のようにして求める。すなわち、仮焼アルミナの粒度分布をレーザー回折散乱式粒度分布測定装置で測定して得られた粒径が３μｍ以下の割合をＡ質量％とし、粒径が８ｍｍ以下の耐火原料１００質量％に占める仮焼アルミナの割合をＢ質量％とすると、粒径が８ｍｍ以下の耐火材料１００質量％に占める割合としての、粒径が３μｍ以下の仮焼アルミナの含有量はＡ×Ｂ／１００質量％となる。なお、仮焼アルミナを含有した耐火原料を使用する場合は、その耐火原料に含まれる粒径が３μｍ以下の仮焼アルミナの量を合算する。 Here, the content of calcined alumina having a particle size of 3 μm or less as a proportion of 100% by mass of the refractory raw material having a particle size of 8 mm or less is determined as follows. That is, the particle size distribution of calcined alumina measured with a laser diffraction / scattering particle size distribution analyzer is A mass%, and the ratio of the particle diameter of 3 μm or less is 100% by mass of the refractory raw material having a particle diameter of 8 mm or less. When the ratio of the calcined alumina is B mass%, the content of the calcined alumina having a particle diameter of 3 μm or less as a ratio to 100 mass% of the refractory material having a particle diameter of 8 mm or less is A × B / 100 mass%. Become. In addition, when using the refractory raw material containing calcined alumina, the quantity of the calcined alumina whose particle size contained in the refractory raw material is 3 micrometers or less is added together.
本発明の不定形耐火物において、骨材となる粒径が０．１ｍｍ超８ｍｍ以下の耐火原料は、アルミナ原料及びスピネル原料の少なくとも１種を主として構成できる。典型的には、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で、０．１ｍｍ超８ｍｍ以下のアルミナ原料及びスピネル原料の少なくとも１種が５０〜７５質量％である。 In the amorphous refractory according to the present invention, the refractory raw material having a particle size of more than 0.1 mm and not more than 8 mm, which is an aggregate, can mainly constitute at least one of an alumina raw material and a spinel raw material. Typically, at least one of the alumina raw material and the spinel raw material having a particle diameter of 8 mm or less in 100% by mass of 8 mm or less and an alumina raw material and a spinel raw material of 0.1 mm or more and 8 mm or less is 50 to 75% by mass.
以上の本発明の不定形耐火物に好適に使用できる耐火原料を例示すると、以下のとおりである。 Examples of the refractory raw material that can be suitably used for the above-mentioned amorphous refractory of the present invention are as follows.
アルミナ原料としては、電融あるいは焼結によって製造され粒度調整された原料と、仮焼アルミナと呼ばれているバイヤー法で製造された原料を使用する。電融あるいは焼結によって製造され粒度調整されたアルミナ原料は、Ａｌ２Ｏ３含有量が９０質量％以上、好ましくは９９質量％以上のものを使用する。仮焼アルミナは、reactive aluminaあるいはcalcined aluminaと呼ばれている原料である。 As the alumina raw material, a raw material manufactured by electromelting or sintering and having a particle size adjusted, and a raw material manufactured by a Bayer method called calcined alumina are used. The alumina raw material produced by electromelting or sintering and adjusted in particle size has an Al 2 O 3 content of 90% by mass or more, preferably 99% by mass or more. Calcinated alumina is a raw material called reactive alumina or calcined alumina.
スピネル原料としては、ＭｇＯ−Ａｌ２Ｏ３系の化合物で、化学組成がＭｇＯ・Ａｌ２Ｏ３の化学量論組成及びＭｇＯあるいはＡｌ２Ｏ３が過剰に固溶した非化学量論組成の化合物であり、電融あるいは焼結によって製造され粒度調整された原料を使用する。 As the spinel raw material, a MgO—Al 2 O 3 based compound having a chemical composition of MgO · Al 2 O 3 and a non-stoichiometric composition in which MgO or Al 2 O 3 is excessively dissolved in solid solution A raw material that is manufactured by electromelting or sintering and whose particle size is adjusted is used.
マグネシア原料としては、電融あるいは焼結によって製造され粒度調整された原料を使用する。乾燥時にマグネシア原料が消化して体積膨張による亀裂が発生しないように、耐消化性が高いマグネシア原料を使用することが好ましい。耐消化性が高いマグネシア原料とは、不純物であるＣａＯとＳｉＯ２とでＣａＯ／ＳｉＯ２が低いもの、破砕面を持たないもの、表面コーティングされたもの等である。 As the magnesia raw material, a raw material which is manufactured by electromelting or sintering and whose particle size is adjusted is used. It is preferable to use a magnesia raw material having high digestion resistance so that the magnesia raw material is digested during drying and cracks due to volume expansion do not occur. The digestion resistant high magnesia raw material, those CaO and low CaO / SiO 2 in the SiO 2 which is an impurity, having no fractured plane, it is like those surface coating.
マグネシア原料は使用中にアルミナ原料と反応してスピネルを生成するので、細かいマグネシア原料を使用すると生成するスピネルが微細になって耐食性と耐スラグ浸潤性が高まり、粗いマグネシア原料を使用すると体積膨張を示すスピネル生成の速度が遅くなって不定形耐火物が継続した残存膨張性を示して亀裂が少なくなる。 The magnesia raw material reacts with the alumina raw material during use to produce spinel, so if the fine magnesia raw material is used, the generated spinel becomes finer and corrosion resistance and slag infiltration resistance increase, and if the coarse magnesia raw material is used, volume expansion occurs. The rate of spinel formation shown is slowed down, and the irregular refractory exhibits continued residual expansivity, resulting in fewer cracks.
シリカフラワーは、シリカヒューム、ヒュームドシリカ、マイクロシリカ、蒸発シリカ、あるいは、シリカダスト等と呼ばれる粒径が１μｍ以下の非晶質のＳｉＯ２質原料で、Ｓｉ、Ｆｅ−Ｓｉ、ＺｒＯ２等の製造時に発生するＳｉＯガスが空気中で酸化して生成したものである。シリカフラワーは、アルミナ−スピネル−マグネシア質不定形耐火物において、マグネシア原料の消化防止、スピネル生成による膨張の低減、使用時のクリープ性の付与等の目的で、粒径が８ｍｍ以下の耐火材料１００質量％に占める割合として、２質量％以下の範囲で使用することが好ましい。 Silica flour is an amorphous SiO 2 raw material with a particle size of 1 μm or less called silica fume, fumed silica, micro silica, evaporated silica, or silica dust, and is made of Si, Fe—Si, ZrO 2, etc. The SiO gas generated during production is generated by oxidation in air. Silica flour is an alumina-spinel-magnesia amorphous refractory material with a particle size of 8 mm or less for the purpose of preventing digestion of magnesia raw material, reducing expansion due to spinel formation, and imparting creep properties during use. It is preferable to use it in a range of 2% by mass or less as a proportion of mass%.
また、本発明の不定形耐火物の耐火原料としては、使用済の耐火れんが、あるいは不定形耐火物を再利用した、いわゆるリサイクル原料を使用することもできる。このリサイクル原料としては、アルミナ−スピネル質、アルミナ−マグネシア質、あるいはアルミナ−スピネル−マグネシア質の使用済の耐火れんがや、不定形耐火物を再利用することが好ましい。 In addition, as the refractory raw material of the amorphous refractory of the present invention, used refractory bricks or so-called recycled raw materials obtained by reusing the irregular refractory can be used. As the recycled material, it is preferable to reuse used refractory bricks or amorphous refractories of alumina-spinel, alumina-magnesia, or alumina-spinel-magnesia.
本発明の不定形耐火物では、亀裂の伸展を防いで亀裂や剥離の発生を少なくする、あるいは、緻密で大きな骨材によって耐食性を高める目的で、粒径が８ｍｍより大きい耐火原料を使用することも可能である。ただし、本発明では、上述の理由から粒径が８ｍｍ以下の耐火原料を１００質量％として、この１００質量％に占める割合で、ＣａＯ量、スピネル量等を規定する。 The amorphous refractory material of the present invention uses a refractory raw material having a particle size larger than 8 mm in order to prevent cracks from extending and reduce the occurrence of cracks and peeling, or to increase the corrosion resistance with a dense and large aggregate. Is also possible. However, in the present invention, the refractory raw material having a particle size of 8 mm or less is defined as 100% by mass for the above-described reason, and the CaO amount, spinel amount, etc. are defined in the proportion of 100% by mass.
また、本発明の不定形耐火物では、その他の耐火原料として、ジルコニア、ムライト、ジルコニア−アルミナ、クロミア等を使用することも可能であるが、これらの使用量は、粒径が８ｍｍ以下の耐火原料１００質量％に占める割合で１０質量％以下にすることが好ましい。 In addition, in the amorphous refractory material of the present invention, zirconia, mullite, zirconia-alumina, chromia, etc. can be used as other refractory raw materials. It is preferable to make it 10 mass% or less in the ratio which occupies for 100 mass% of raw materials.
以上説明した本発明の不定形耐火物は、流し込み施工、湿式吹き付け施工に好適に使用することができる。 The amorphous refractory of the present invention described above can be suitably used for casting construction and wet spraying construction.
表１は、本発明の実施例１〜２１と比較例１〜５の原料構成を示す。 Table 1 shows the raw material structures of Examples 1 to 21 and Comparative Examples 1 to 5 of the present invention.
耐火原料としては、Ａｌ２Ｏ３含有量が９９．３〜９９．７質量％で粒度範囲が８−０．１ｍｍと０．１ｍｍ以下の焼結アルミナ、ＭｇＯ含有量が４〜６質量％で粒度範囲が８−０．１ｍｍの焼結スピネル、ＭｇＯ含有量が２６〜２８質量％で粒度範囲が１−０．３ｍｍと０．１ｍｍ以下の焼結スピネル、粒径３μｍ以下の含有量が１８．２質量％の仮焼アルミナＡ、粒径３μｍ以下の含有量が９３．６質量％の仮焼アルミナＢ、ＭｇＯ含有量が９５．０〜９５．５質量％で粒度範囲が１−０．３ｍｍと０．１ｍｍ以下の焼結マグネシア、ＳｉＯ２含有量が９８．４質量％で平均粒径が０．２μｍのシリカフラワーを使用した。同じく耐火原料であるスピネル含有アルミナセメント及びアルミナセメントは、それぞれ、ケルネオス社のＣＭＡ７２及びＳＥＣＡＲ７１を使用した。ＣＭＡ７２とＳＥＣＡＲ７１は、９９質量％が０．１ｍｍ以下であった。また、減水剤としてポリアクリル酸ソーダを、０．１質量％使用した。上記の減水剤を含む耐火原料の合計が１００質量％である。 As a refractory raw material, Al 2 O 3 content is 99.3 to 99.7 mass%, particle size range is 8-0.1 mm and sintered alumina with 0.1 mm or less, MgO content is 4 to 6 mass% Sintered spinel with a particle size range of 8-0.1 mm, sintered spinel with a MgO content of 26-28% by mass and a particle size range of 1-0.3 mm and 0.1 mm or less, and a content of particle size of 3 μm or less of 18 .2% by mass of calcined alumina A, a particle size of 3 μm or less of calcined alumina B with a content of 93.6% by mass, a MgO content of 95.0-95.5% by mass and a particle size range of 1-0. Sintered magnesia of 3 mm and 0.1 mm or less, and silica flour having a SiO 2 content of 98.4% by mass and an average particle size of 0.2 μm were used. Similarly, the spinel-containing alumina cement and alumina cement, which are refractory raw materials, were CMA 72 and SECAR 71 manufactured by Kerneos, respectively. As for CMA72 and SECAR71, 99 mass% was 0.1 mm or less. Moreover, 0.1 mass% of sodium polyacrylate was used as a water reducing agent. The total of the refractory raw materials including the water reducing agent is 100% by mass.
表１中の「セメント中のＣａＯ」は、上記耐火原料１００質量％に占める割合としての、スピネル含有アルミナセメント（ＣＭＡ７２）とアルミナセメント（ＳＥＣＡＲ７１）中のＣａＯ合計量の割合を質量％で示す。
「スピネル含有アルミナセメント中のスピネル」は、上記耐火原料１００質量％に占める割合としての、スピネル含有アルミナセメントに含まれるスピネル量の割合を質量％で示す。
「０．１ｍｍ以下のスピネル」は、上記耐火原料１００質量％に占める割合としての、スピネル含有アルミナセメントに含まれるスピネルと粒径０．１ｍｍ以下のスピネル原料（焼結スピネル）との合計量の割合を質量％で示す。
「０．１ｍｍ以下のマグネシア」は、上記耐火原料１００質量％に占める割合としての、粒径０．１ｍｍ以下のマグネシア原料（焼結マグネシア）の割合を質量％で示す。
ここで、粒径０．１ｍｍ以下の量とは、開き目が０．１００ｍｍの篩下の量である。
“CaO in cement” in Table 1 indicates the ratio of the total amount of CaO in spinel-containing alumina cement (CMA72) and alumina cement (SECAR71) as a ratio in 100% by mass of the refractory raw material.
“Spinel in spinel-containing alumina cement” indicates the proportion of the amount of spinel contained in the spinel-containing alumina cement as a proportion in 100% by mass of the refractory raw material.
“Spinel of 0.1 mm or less” is the total amount of the spinel contained in the spinel-containing alumina cement and the spinel material (sintered spinel) having a particle size of 0.1 mm or less as a proportion of 100% by mass of the refractory raw material. The ratio is shown by mass%.
“0.1 mm or less magnesia” indicates the ratio of the magnesia raw material (sintered magnesia) having a particle size of 0.1 mm or less in terms of mass%, as a ratio to 100 mass% of the refractory raw material.
Here, the amount having a particle size of 0.1 mm or less is the amount under the sieve having an opening of 0.100 mm.
表１中の「３μｍ以下の仮焼アルミナ」は、上記耐火原料１００質量％に占める割合としての、３μｍ以下の仮焼アルミナ量の割合を質量％で示す。ここで、３μｍ以下の仮焼アルミナ量は、仮焼アルミナＡと仮焼アルミナＢの粒度分布をレーザー回折散乱式粒度分布測定装置で測定し、それぞれの３μｍ以下の量と仮焼アルミナＡと仮焼アルミナＢの使用量から計算した値である。 The “calcined alumina of 3 μm or less” in Table 1 represents the ratio of the amount of calcined alumina of 3 μm or less as a percentage of 100% by mass of the refractory raw material in mass%. Here, the amount of calcined alumina of 3 μm or less is determined by measuring the particle size distribution of calcined alumina A and calcined alumina B with a laser diffraction scattering type particle size distribution measuring device. It is a value calculated from the amount of calcined alumina B used.
表１の各原料構成による不定形耐火物の試験片を作製し、それぞれ、溶損深さ、スラグ浸潤深さ、曲げ強度及び耐熱スポーリング性を評価した。試験片は、表１の各原料を鋳込み成形するのに適正な水分量で混練し、所定形状の枠内に鋳込み、枠に２Ｇの振動を加えて十分に脱気し、２４時間養生して得た。 Test pieces of irregular refractories having the respective raw material configurations shown in Table 1 were prepared, and the melting depth, slag infiltration depth, bending strength, and heat spalling resistance were evaluated. The test piece is kneaded with a proper amount of moisture to cast and mold each raw material in Table 1, cast into a frame of a predetermined shape, sufficiently degassed by applying 2G vibration to the frame, and cured for 24 hours. Obtained.
溶損深さは、転炉スラグを用いて１６５０℃で１０時間のスラグ回転浸食試験を実施し、溶損深さが７ｍｍ以下は○、７ｍｍより大きく１０ｍｍ以下は△、１０ｍｍより大きいものは×とした。溶損深さは、耐食性の指標である。 The erosion depth was measured by performing a slag rotation erosion test for 10 hours at 1650 ° C. using a converter slag. The erosion depth was 7 mm or less, ◯, greater than 7 mm and 10 mm or less, Δ It was. The erosion depth is an index of corrosion resistance.
スラグ浸潤深さは、溶損深さを測定したスラグ回転浸食試験において、スラグ浸潤深さが２ｍｍ以下は○、２ｍｍより大きく４ｍｍ以下は△、４ｍｍより大きいものは×とした。 In the slag rotation erosion test in which the erosion depth was measured, the slag infiltration depth was evaluated as ◯ when the slag infiltration depth was 2 mm or less, and △ when 2 mm or more and 4 mm or less.
曲げ強度は、４０×４０×１６０ｍｍ形状の試験片を上記手法で養生し、その後脱枠して１１０℃で２４時間乾燥し、１２００℃で３時間焼成後に測定した値が１５ＭＰａ以上は○、１５ＭＰａより小さく１０ＭＰａ以上は△、１０ＭＰａより小さいものは×とした。 The bending strength was determined by curing a test piece having a shape of 40 × 40 × 160 mm by the above method, then removing the frame, drying it at 110 ° C. for 24 hours, and firing at 1200 ° C. for 3 hours. Smaller than 10 MPa, Δ is smaller than 10 MPa, and x.
耐熱スポーリング性は、２３０×１１４×６５ｍｍ形状の試験片を上記手法で養生し、その後脱枠して１１０℃で２４時間乾燥し、３５０℃で６時間熱処理した試験片を用いて加熱と冷却を繰り返し、亀裂の発生状況を観察した。具体的には、１４００℃に加熱した電気炉で１１４×６５ｍｍ面を３０分間加熱してから３０分間空冷する操作を５回繰り返し、亀裂の発生が軽微であったものは○、やや亀裂が発生したものは△、大きな亀裂が発生したものは×とした。 The heat spalling property is obtained by heating and cooling using a test piece which is a 230 × 114 × 65 mm-shaped test piece cured by the above method, then de-framed, dried at 110 ° C. for 24 hours, and heat-treated at 350 ° C. for 6 hours. Was repeated and the occurrence of cracks was observed. Specifically, the operation of heating the 114 × 65 mm surface for 30 minutes in an electric furnace heated to 1400 ° C. for 30 minutes and then air-cooling for 30 minutes was repeated 5 times. The case where the crack was generated was indicated by Δ, and the case where a large crack occurred was indicated by ×.
総合評価は、溶損深さ、スラグ浸潤深さ、曲げ強度、耐熱スポーリングの各評価において、全て○であったものは◎、それら以外で×がなくて○が２個以上のものは○、それら以外で×がないものは△、×があったものは×とした。 Comprehensive evaluation is ◎ for all evaluations of erosion depth, slag infiltration depth, bending strength, and heat-resistant spalling. In addition to these, the case where there was no x was Δ, and the case where there was x was x.
実施例１〜２１は本発明の実施例であり、溶損深さ、スラグ浸潤深さ、曲げ強度及び耐熱スポーリング性の各評価に×がなく、耐食性と耐スラグ浸潤性が高く、高強度で、かつ耐熱スポーリング性が高い不定形耐火物が得られた。 Examples 1-21 are examples of the present invention, and there is no x in each evaluation of melting depth, slag infiltration depth, bending strength, and heat spalling resistance, corrosion resistance and slag infiltration resistance are high, and high strength In addition, an amorphous refractory having high heat spalling resistance was obtained.
なお、実施例１〜２１のうち、「０．１ｍｍ以下のスピネル」の好ましい範囲（５．５〜２２質量％）から外れた実施例７，１０、「３μｍ以下の仮焼アルミナ」の好ましい範囲（４〜１０質量％）から外れた実施例１８、及びマグネシア原料を使用した実施例のうち「０．１ｍｍ以下のマグネシア」の好ましい範囲（３〜９質量％）から外れた実施例１２，１６は、他の実施例に比べると各評価の結果が劣る傾向にあるが、各評価に×はなく、後述する比較例に比べると耐食性と耐スラグ浸潤性が高く、高強度で、かつ耐熱スポーリング性が高い不定形耐火物が得られた。 In addition, in Examples 1-21, Examples 7 and 10 deviating from the preferable range (5.5 to 22% by mass) of “0.1 mm or less spinel”, “Preferable range of“ calcined alumina of 3 μm or less ”” Examples 18 and 16 deviating from the preferred range (3 to 9% by mass) of “0.1 mm or less” in Example 18 deviating from (4 to 10% by mass) and Examples using magnesia raw materials The results of each evaluation tend to be inferior compared to the other examples, but there is no x in each evaluation. Compared to the comparative examples described later, the corrosion resistance and slag infiltration resistance are high, the strength is high, and the heat resistant slag is high. An amorphous refractory with high poling property was obtained.
比較例１は、スピネル含有アルミナセメントを使用していない例であり、耐食性が低く、スラグ浸潤が大きい。
比較例２は、セメント中のＣａＯとスピネル含有アルミナセメント中のスピネルが本発明の範囲より少ない例であり、強度が低い。
比較例３は、セメント中のＣａＯが本発明の範囲より多い例であり、耐食性が低い。
比較例４は、スピネル含有セメント中のスピネルが本発明の範囲より多い例であり、スラグ浸潤が大きく、耐熱スポーリング性が低い。
比較例５は、セメント中のＣａＯとスピネル含有セメント中のスピネルが本発明の範囲より多い例であり、耐食性が低く、スラグ浸潤が大きく、耐熱スポーリング性が低い。
Comparative Example 1 is an example in which spinel-containing alumina cement is not used, and has low corrosion resistance and large slag infiltration.
Comparative Example 2 is an example in which CaO in the cement and spinel in the spinel-containing alumina cement are less than the scope of the present invention, and the strength is low.
Comparative Example 3 is an example in which the amount of CaO in the cement is greater than the range of the present invention, and the corrosion resistance is low.
Comparative Example 4 is an example in which the amount of spinel in the spinel-containing cement is larger than the range of the present invention, slag infiltration is large, and heat spalling resistance is low.
Comparative Example 5 is an example in which the CaO in the cement and the spinel in the spinel-containing cement are more than the scope of the present invention, and the corrosion resistance is low, the slag infiltration is large, and the heat spalling resistance is low.
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| JPS5678461A (en) * | 1979-11-29 | 1981-06-27 | Sumitomo Cement Co | Manufacture of highly refractory alumina cement |
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| JPH06256064A (en) * | 1993-03-03 | 1994-09-13 | Kurosaki Refract Co Ltd | Dense castable refractory low in water content and capable of being cast |
| JPH06321608A (en) * | 1993-05-14 | 1994-11-22 | Denki Kagaku Kogyo Kk | Cement composition and monolithic refractories incorporating the same |
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