JP2018058720A - Brick for blast furnace hearth, blast furnace hearth using the same, and method for producing brick for blast furnace hearth - Google Patents
Brick for blast furnace hearth, blast furnace hearth using the same, and method for producing brick for blast furnace hearth Download PDFInfo
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- 239000011449 brick Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 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 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000004898 kneading Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 47
- 239000002184 metal Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 14
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 12
- 239000003830 anthracite Substances 0.000 description 12
- 230000003628 erosive effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum compound Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000002808 connective tissue Anatomy 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Blast Furnaces (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
Description
本発明は、高炉において羽口より下の炉床に使用される高炉炉床用れんが及びこれを使用した高炉炉床、並びに高炉炉床用れんがの製造方法に関する。 The present invention relates to a blast furnace hearth brick used for a hearth below a tuyere in a blast furnace, a blast furnace hearth using the same, and a method for producing a brick for a blast furnace hearth.
高炉炉床には、主として、黒鉛を骨材とする炭素質れんが、あるいはアルミナを骨材とするアルミナ質れんがが使用されているが、炉寿命を支配する要因の１つとしてこれらの高炉炉床用れんがの損耗が挙げられる。 For the blast furnace hearth, carbonaceous bricks using graphite as an aggregate or alumina bricks using alumina as an aggregate are mainly used, and these blast furnace hearths are one of the factors governing the life of the furnace. The wear of bricks is mentioned.
例えば高炉の炉床部の内張り材としては、炭素質れんが（ブロック）が主流となっているが、炭素成分の多いれんがは、高炉炉床部での使用時に炭素が溶銑中へ溶け出しやすく耐溶銑性が良くない。そのため、炉外から内張り材の冷却を強化して、れんが稼働面に溶銑粘稠層を形成し、この溶銑粘稠層によって炭素質れんがから溶銑中への炭素の溶け出しを防止して耐溶銑性を確保している。しかしながら、このような炉外からの冷却は、大きいエネルギーロスをもたらすことになる。 For example, carbonaceous bricks (blocks) are the mainstream lining material for the hearth of the blast furnace, but bricks with a high carbon content tend to melt into the hot metal when used in the blast furnace hearth. The hot metal is not good. Therefore, the cooling of the lining material from the outside of the furnace is strengthened to form a hot metal viscous layer on the working surface of the brick, and this hot metal viscous layer prevents carbon from leaching from the carbon brick into the hot metal. The sex is secured. However, such cooling from outside the furnace results in a large energy loss.
そこで、炭素を少なくし溶銑中へ溶け出しにくいアルミナを主体とするアルミナ質れんがも近年使用されてきている。特に、化学式Ｓｉ６−ＺＡｌＺＯＺＮ８−Ｚで表されるβ’−サイアロンをマトリックス部に含むサイアロンボンドアルミナれんがは、炭素をほとんど含まないため、耐溶銑性に優れ、しかも高炉中で発生するスラグに対する耐食性（耐スラグ性）に優れている。 In view of this, alumina-based bricks mainly composed of alumina, which has less carbon and is difficult to dissolve into hot metal, have been used in recent years. In particular, the formula Si 6-Z Al Z O Z N sialon bond alumina bricks containing represented β'- sialon in 8-Z in the matrix portion, because they contain little carbon, excellent solvent resistance to molten iron resistance, moreover blast furnace Excellent corrosion resistance (slag resistance) against slag generated in
例えば特許文献１には、マトリックス部（結合基質）に、Ｚ値（β’−サイアロンの化学式Ｓｉ６−ＺＡｌＺＯＺＮ８−ＺにおけるＺ値のことをいう。以下同じ。）が０．５〜４のβ’−サイアロンを１２〜４５質量％含有するサイアロンボンドアルミナれんがが開示されている。しかし、この特許文献１のサイアロンボンドアルミナれんがでは、そのマトリックス部に含まれるβ’−サイアロン中のＳｉが少しずつ溶銑中へ溶け出すため、れんがの損耗が進み、耐溶銑性が十分ではない。 For example, Patent Document 1, the matrix portion (bound substrate), Z value (refers to a Z value in β'- sialon of formula Si 6-Z Al Z O Z N 8-Z. Hereinafter the same.) 0 A sialon bond alumina brick containing 12 to 45 mass% of β-4 sialon of 5 to 4 is disclosed. However, in the sialon bond alumina brick of Patent Document 1, since the Si in β′-sialon contained in the matrix portion gradually melts into the hot metal, the wear of the brick proceeds and the hot metal resistance is not sufficient.
そこで、特許文献２では、窒化アルミニウム及び／又は酸炭化アルミニウムを結合組織とし主成分がアルミナから成るれんが（アルミニウム化合物結合れんが）が開示され、Ｓｉをほとんど含有しないため耐溶銑性に優れるとされている。さらに、このれんがにおいて炭素質原料を５〜３０質量％使用したれんがも開示されている。そして炭素質原料としては特に仮焼無煙炭は、炭素質原料の中でも天然黒鉛や人造黒鉛等と比較すると耐食性に優れる点でより好ましいとされている。 Therefore, Patent Document 2 discloses a brick (aluminum compound-bonded brick) composed mainly of alumina with aluminum nitride and / or aluminum oxycarbide as a connective structure, and is considered to have excellent hot metal resistance because it contains almost no Si. Yes. Furthermore, the brick which uses 5-30 mass% of carbonaceous raw materials in this brick is also disclosed. As the carbonaceous raw material, calcined anthracite is particularly preferable among the carbonaceous raw materials because it has excellent corrosion resistance as compared with natural graphite and artificial graphite.
また、特許文献３においても、炭素質原料中で仮焼無煙炭が耐溶銑侵食性に優れていると記載されている。 Patent Document 3 also describes that calcined anthracite is excellent in hot metal erosion resistance in a carbonaceous raw material.
しかしながら、特許文献２の高炉炉床用アルミニウム化合物結合れんがにおいて、仮焼無煙炭を使用した場合には耐溶銑性の低下が大きくしかも耐スラグ性もまだ不十分であり、高炉の炉床部の内張り材としてはさらなる改善が望まれている。 However, in the aluminum compound bonded brick for blast furnace hearth of Patent Document 2, when calcined anthracite is used, the deterioration of hot metal resistance is large and the slag resistance is still insufficient. Further improvement is desired as a material.
本発明が解決しようとする課題は、耐溶銑性と耐スラグ性を向上させた高炉炉床用れんがを提供しさらに高炉炉床の寿命を向上することにある。 The problem to be solved by the present invention is to provide a blast furnace hearth brick having improved hot metal resistance and slag resistance, and to further improve the life of the blast furnace hearth.
本発明者等は、高炉炉床用のアルミニウム化合物結合れんがにおいて、耐溶銑性と耐スラグ性をさらに向上するために、種々の炭素質原料の影響について検討した。従来、鱗状黒鉛と仮焼無煙炭とを比較した場合、一般的に鱗状黒鉛の方が結晶性が高く不純物も少ないため耐スラグ性に優れるとされ、逆に耐溶銑性は鱗状黒鉛が仮焼無煙炭よりも劣るとされていた（特許文献２や特許文献３）。ところが、本発明者等による検討結果では、０．２ｍｍ以下の微粉で１０質量％以下の少ない領域でかつ窒化アルミニウムボンド及び／又は酸炭化アルミニウムボンドと共存する場合には、従来とは逆に鱗状黒鉛が仮焼無煙炭よりも耐溶銑性に優れるという新しい知見が得られた。しかも耐スラグ性は仮焼無煙炭よりも格段に優れる結果となった。その結果、粒径の小さな鱗状黒鉛を少量使用することで耐溶銑性と耐スラグ性とを同時に高い次元で満足できることを知見した。 The present inventors examined the influence of various carbonaceous raw materials in order to further improve the hot metal resistance and slag resistance in aluminum compound bonded bricks for blast furnace hearths. Conventionally, when scaly graphite and calcined anthracite are compared, generally scaly graphite is superior in slag resistance because it has higher crystallinity and less impurities, and conversely, scaly graphite is calcined anthracite. (Patent Literature 2 and Patent Literature 3). However, as a result of investigations by the present inventors, when a fine powder of 0.2 mm or less is present in a small region of 10 mass% or less and coexists with an aluminum nitride bond and / or an aluminum oxycarbide bond, it is contrary to the conventional case. A new finding was obtained that graphite is more resistant to hot metal than calcined anthracite. In addition, the slag resistance was much better than calcined anthracite. As a result, it has been found that the use of a small amount of scaly graphite having a small particle size can satisfy both hot metal resistance and slag resistance at a high level at the same time.
すなわち、本発明の要旨は、アルミナを８０質量％以上９５量％以下、アルミニウムを１質量％以上１５質量％以下、及び粒度が０．２ｍｍ以下の鱗状黒鉛を４質量％以上１０質量％以下含有し、しかもＳｉ成分が３．０質量％以下（０を含む）である耐火原料配合物に、バインダーを添加して混練し成形後、窒素雰囲気下又は炭素粒中で１０００℃以上で焼成して得られる高炉炉床用れんがである。 That is, the gist of the present invention is that 80% by mass or more and 95% by mass or less of alumina, 1% by mass or more and 15% by mass or less of aluminum, and 4% by mass or more and 10% by mass or less of scaly graphite having a particle size of 0.2 mm or less. In addition, a binder is added to a refractory raw material composition having an Si component of 3.0% by mass or less (including 0), kneaded and molded, and then fired at 1000 ° C. or higher in a nitrogen atmosphere or in carbon particles. The resulting brick for the blast furnace hearth.
鱗状黒鉛は耐スラグ性を向上するために使用し、鱗状黒鉛の粒度が０．２ｍｍを超えると耐スラグ性が不十分になる。また、耐火原料配合物中の粒度が０．２ｍｍ以下の鱗状黒鉛の含有量が４質量％未満では耐スラグ性が不十分となり、１０質量％を超えると耐溶銑性が不十分となる。 Scaly graphite is used to improve slag resistance, and when the particle size of the flaky graphite exceeds 0.2 mm, the slag resistance becomes insufficient. Further, when the content of the scaly graphite having a particle size of 0.2 mm or less in the refractory raw material composition is less than 4% by mass, the slag resistance is insufficient, and when it exceeds 10% by mass, the hot metal resistance is insufficient.
なお、粒度が０．２ｍｍを超える鱗状黒鉛は使用しないことが好ましいが、１質量％以下であれば悪影響は小さいことから使用可能である。また、鱗状黒鉛以外の炭素質原料は鱗状黒鉛よりも耐スラグ性に劣るために使用しないことが好ましいが、これも１質量％以下であれば悪影響は小さいことから使用可能である。 In addition, it is preferable not to use scaly graphite having a particle size exceeding 0.2 mm. Moreover, it is preferable not to use carbonaceous raw materials other than scaly graphite because they are inferior in slag resistance to scaly graphite.
耐火原料配合物においてアルミナは優れた耐溶銑性を有するために８０質量％以上９５質量％以下含有する。８０質量％未満では耐溶銑性が不十分となり、９５質量％を超えると相対的に鱗状黒鉛及び窒化アルミニウム及び／又は酸炭化アルミニウムが少なくなるため、窒化アルミニウム及び／又は酸炭化アルミニウム並びに鱗状黒鉛による耐スラグ性と耐溶銑性の効果が低下する。 In the refractory raw material composition, alumina is contained in an amount of 80% by mass or more and 95% by mass or less in order to have excellent hot metal resistance. If it is less than 80% by mass, the hot metal resistance becomes insufficient, and if it exceeds 95% by mass, the amount of scaly graphite and aluminum nitride and / or aluminum oxycarbide is relatively small. Therefore, it depends on aluminum nitride and / or aluminum oxycarbide and scaly graphite. The effect of slag resistance and hot metal resistance decreases.
アルミニウムは焼成後に窒化アルミニウム及び／又は酸炭化アルミニウムとなるため耐溶銑性及び耐スラグ性に優れることから含有させ、１質量％未満では耐溶銑性及び耐スラグ性が不十分となり１５質量％を超えると相対的にアルミナの含有量が少なくなるため耐溶銑性が低下する。 Since aluminum becomes aluminum nitride and / or aluminum oxycarbide after firing, it is included because it has excellent hot metal resistance and slag resistance, and if it is less than 1% by mass, the hot metal resistance and slag resistance become insufficient and exceeds 15% by mass. Since the content of alumina is relatively small, the hot metal resistance is lowered.
耐火原料配合物中のアルミナ原料や鱗状黒鉛には少量のＳｉＯ２が含有されているが、これらの原料に含まれるＳｉＯ２に由来するＳｉ成分、あるいは耐火原料配合物に少量含まれる可能性のあるＳｉ３Ｎ４やＳｉＣなどに由来するＳｉ成分は溶銑中に溶け出すため耐溶銑性を低下させることになる。このため耐火原料配合物中のＳｉ成分は無いことが最も良いが、３質量％以下、好ましくは１質量％以下に抑える。この範囲であれば耐食性に与える悪影響は小さいことから使用することもできる。 The alumina raw material and scaly graphite in the refractory raw material composition contain a small amount of SiO 2, but the Si component derived from SiO 2 contained in these raw materials or the possibility of being contained in a small amount in the refractory raw material composition Since the Si component derived from certain Si 3 N 4 , SiC or the like is dissolved in the hot metal, the hot metal resistance is lowered. For this reason, it is best that there is no Si component in the refractory raw material composition, but it is limited to 3% by mass or less, preferably 1% by mass or less. If it is this range, since the bad influence on corrosion resistance is small, it can also be used.
本発明の高炉炉床用れんがは、以上のような耐火原料配合物に、バインダーを添加して混練し成形後、窒素雰囲気下又は炭素粒中で１０００℃以上、より好ましくは１３００℃以上１５００℃以下で焼成することによって得られる。 The brick for blast furnace hearth of the present invention is added to a refractory raw material composition as described above, kneaded and molded, and then in a nitrogen atmosphere or in carbon grains, 1000 ° C or higher, more preferably 1300 ° C or higher and 1500 ° C. It is obtained by firing below.
このようにして得られた本発明の高炉炉床用れんがは、れんがの鉱物組織が、コランダムが７７〜９５質量％、窒化アルミニウム結晶及び／又は酸炭化アルミニウム結晶が１〜１８質量％、並びに鱗状黒鉛が４〜１０質量％なる。しかも、れんが中のＳｉ成分は３質量％以下（０を含む）となる。また、これらの鉱物相以外には非晶質相を１〜１０質量％含むことができる。 The brick for the blast furnace hearth of the present invention thus obtained has a brick mineral structure of 77 to 95% by mass of corundum, 1 to 18% by mass of aluminum nitride crystals and / or aluminum oxycarbide crystals, and scale-like. Graphite is 4 to 10% by mass. Moreover, the Si component in the brick is 3% by mass or less (including 0). Moreover, 1-10 mass% of amorphous phases other than these mineral phases can be included.
ここで非晶質相とは、主としてバインダーなどに起因する非晶質炭素であるが、その他にも黒鉛に含まれるいわゆる灰分、アルミナに含まれる非晶質酸化物（ＳｉＯ２、ＴｉＯ２など）等を含む。 Here, the amorphous phase is amorphous carbon mainly resulting from a binder or the like, but in addition, so-called ash contained in graphite, amorphous oxide contained in alumina (SiO 2 , TiO 2, etc.) Etc.
本発明の高炉炉床用れんがは、高炉において羽口よりも下の部位である炉床部にライニングすることで高炉の耐用性を大幅に延長することができる。 The brick for a blast furnace hearth of the present invention can significantly extend the durability of the blast furnace by lining it in the hearth part which is a part below the tuyere in the blast furnace.
本発明のれんがは、耐溶銑性及び耐スラグに優れるため、高炉炉床の寿命を向上させることができる。 Since the brick of the present invention is excellent in hot metal resistance and slag resistance, the life of the blast furnace hearth can be improved.
本発明の耐火原料配合物として使用されるアルミナは、通常の耐火物の原料として使用されているものであれば問題なく使用することが可能で、電融アルミナ、焼結アルミナ、仮焼アルミナ等を使用することができる。ただし、ＳｉＯ２の含有量は少ないほど耐食性が向上し、好ましくはＳｉＯ２の含有量が１質量％以下、より好ましくは０．５質量％以下のアルミナを使用する。またＡｌ２Ｏ３純度としては溶銑に対する耐食性の面から９０質量％以上のものを使用することが好ましく、９８質量％以上のものがより好ましい。 Alumina used as the refractory raw material composition of the present invention can be used without problems as long as it is used as a raw material for ordinary refractories, such as fused alumina, sintered alumina, calcined alumina, etc. Can be used. However, the smaller the SiO 2 content, the better the corrosion resistance. Preferably, alumina having a SiO 2 content of 1% by mass or less, more preferably 0.5% by mass or less is used. In addition, the Al 2 O 3 purity is preferably 90% by mass or more, more preferably 98% by mass or more from the viewpoint of corrosion resistance to hot metal.
本発明で使用されるアルミニウムとしては、通常、耐火物に使用されている粉末状のものであれば問題なく使用することができ、微粉で使用する方がより反応性が高い点から好ましい。この点からアルミニウム粉末の粒度としては７４μｍ以下であることがより好ましい。粉末状アルミニウムはその製法の違いにより、アトマイズ粉とフレーク粉とが市販されている。本発明ではどちらのものでも使用可能である。 As the aluminum used in the present invention, it can be used without any problem as long as it is usually used in a refractory material, and it is preferable to use it in a fine powder because it is more reactive. From this point, the particle size of the aluminum powder is more preferably 74 μm or less. Powdered aluminum is commercially available in atomized powder and flake powder due to the difference in its production method. Either one can be used in the present invention.
本発明において、耐溶銑性と耐スラグ性とを両立させるために炭素質原料としては鱗状黒鉛を使用し、仮焼無煙炭、コークス、ピッチなどは基本的には使用しない。ただし、前述のとおり悪影響を及ぼさない範囲で少量使用することは可能である。ここで、炭素質原料にはバインダーとして使用するフェノール樹脂やタール等の有機バインダーは含まない。 In the present invention, scaly graphite is used as the carbonaceous raw material in order to achieve both hot metal resistance and slag resistance, and calcined anthracite, coke, pitch, etc. are basically not used. However, as described above, it can be used in a small amount within a range that does not have an adverse effect. Here, the carbonaceous raw material does not include an organic binder such as a phenol resin or tar used as a binder.
鱗状黒鉛は一般的に耐火物の原料として使用されているものを使用することができ、その粒度は０．２ｍｍ以下のものを使用する。ここで粒度とは篩目のことであり、粒度が０．２ｍｍ以下とは０．２ｍｍの篩目を通過したものをいう。なお、粉砕処理したものも使用可能である。 As the scaly graphite, those generally used as raw materials for refractories can be used, and those having a particle size of 0.2 mm or less are used. Here, the particle size means a sieve mesh, and the particle size of 0.2 mm or less means a material that has passed a 0.2 mm mesh. A pulverized product can also be used.
本発明の耐火原料配合物の主成分は、アルミナとアルミニウムと鱗状黒鉛とで構成されるが、窒化アルミニウム、Ａｌ２ＯＣ、Ａｌ４Ｏ４Ｃ、あるいはジルコニアを１０質量％以下で使用しても良い。ただし、耐火原料配合物中のＳｉ成分は３質量％以下にする必要がある。 The main components of the refractory raw material composition of the present invention are composed of alumina, aluminum, and scaly graphite, but aluminum nitride, Al 2 OC, Al 4 O 4 C, or zirconia may be used at 10% by mass or less. good. However, the Si component in the refractory raw material composition must be 3% by mass or less.
耐火原料配合物は、これを常法で混練後成形し、必要に応じて乾燥した後、焼成する。混練する際には、耐火物として一般的に使用されているバインダーを使用できる。焼成は窒素雰囲気下又は炭素粒中で行い、１０００℃以上、好ましくは１３００℃〜１５００℃で焼成する。焼成温度が１０００℃よりも低いときは窒化アルミニウム及び／又は酸炭化アルミニウムの生成が不十分であり耐溶銑性と耐スラグ性の効果が得られない。焼成温度が１５００℃よりも高いときは窒化アルミニウム及び／又は酸炭化アルミニウムの生成は十分であるがそれらの結晶成長が過剰になり耐溶銑性と耐スラグ性の効果が減少する。 The refractory raw material composition is kneaded and molded by a conventional method, dried as necessary, and then fired. When kneading, a binder generally used as a refractory can be used. Firing is performed in a nitrogen atmosphere or in carbon grains, and is performed at 1000 ° C. or higher, preferably 1300 ° C. to 1500 ° C. When the firing temperature is lower than 1000 ° C., the formation of aluminum nitride and / or aluminum oxycarbide is insufficient, and the effects of hot metal resistance and slag resistance cannot be obtained. When the firing temperature is higher than 1500 ° C., the formation of aluminum nitride and / or aluminum oxycarbide is sufficient, but their crystal growth becomes excessive, and the effects of hot metal resistance and slag resistance are reduced.
この焼成により、窒化アルミニウム（ＡｌＮ）と、Ａｌ２ＯＣやＡｌ４Ｏ４Ｃのような酸炭化アルミニウムとのうち１つ以上が生成すれば緻密で強力な結合組織を形成し、効果が十分に得られる。 If this firing produces one or more of aluminum nitride (AlN) and aluminum oxycarbide such as Al 2 OC and Al 4 O 4 C, a dense and strong connective structure is formed, and the effect is sufficient can get.
上記製法によって得られる本発明の高炉炉床用れんがの組織は、コランダムが７７〜９５質量％、窒化アルミニウム結晶及び／又は酸炭化アルミニウム結晶が１〜１８質量％、鱗状黒鉛が４〜１０質量％、並びに非晶質相が１〜１０質量％となる。なお、れんが中のＳｉ成分は３質量％以下（０を含む）とする。 The structure of the brick for a blast furnace hearth of the present invention obtained by the above production method is 77 to 95% by mass of corundum, 1 to 18% by mass of aluminum nitride crystal and / or aluminum oxycarbide crystal, and 4 to 10% by mass of scaly graphite. In addition, the amorphous phase is 1 to 10% by mass. In addition, the Si component in the brick is 3% by mass or less (including 0).
本発明の高炉炉床用れんがを高炉炉床に使用する場合、従来のカーボンれんがと併用してあるいは、全て置き換えて使用することができる。具体的には、羽口より下の側壁あるいは炉底に適用することができる。 When the brick for a blast furnace hearth of the present invention is used for a blast furnace hearth, it can be used in combination with a conventional carbon brick or by replacing it all. Specifically, it can be applied to the side wall or the bottom of the furnace below the tuyere.
表１に本発明のれんがの実施例を比較例とともに示す。 Table 1 shows examples of the brick of the present invention together with comparative examples.
各例のれんがは、それぞれ表１に示した耐火原料配合物にバインダーとしてレゾール型フェノール樹脂を適量添加して混練し、オイルプレスでＪＩＳ並形れんが形状の成形体を作製し、２５０℃で加熱処理後、実施例１０以外は窒素気流中で１４００℃で焼成して得た。実施例１０は、炭化珪素材質の耐火れんが製マッフル内に乾燥した成形体を入れてコークス粒中に埋設し大気雰囲気下１４００℃で焼成した。 The bricks in each example were kneaded by adding an appropriate amount of a resol type phenolic resin as a binder to the refractory raw material composition shown in Table 1, and a JIS ordinary brick shaped molded body was produced with an oil press and heated at 250 ° C. After the treatment, except for Example 10, it was obtained by firing at 1400 ° C. in a nitrogen stream. In Example 10, a dried molded body was placed in a muffle made of silicon carbide refractory brick, embedded in coke grains, and fired at 1400 ° C. in an air atmosphere.
原料として使用したアルミナは、Ａｌ２Ｏ３が９８質量％以上、ＳｉＯ２が０．５質量％以下の燒結アルミナを、鱗状黒鉛はＣが９５質量％以上の天然鱗状黒鉛を、仮焼無煙炭はＣが９５質量％以上のものを、カーボンブラックはＣが９５質量％以上のものをそれぞれ使用した。また、Ａｌ（アルミニウム）はフレークタイプを使用した。 Alumina used as a raw material is sintered alumina with 98% by mass or more Al 2 O 3 and 0.5% by mass or less of SiO 2 , scaly graphite is natural scaly graphite with 95% by mass or more of C, calcined anthracite is Carbons with a C content of 95% by mass or more and carbon blacks with a C content of 95% by mass or more were used. Moreover, Al (aluminum) used the flake type.
得られたれんがについて鉱物組成を分析するとともに、物性評価として、見掛気孔率及び圧縮強さ測定するとともに、耐スラグ性及び耐溶銑性を評価した。見掛気孔率はＪＩＳ−Ｒ２２０５、圧縮強さはＪＩＳ−Ｒ２２０６従い測定した。鉱物種の定量はＸ線回折法とＥＰＭＡ法を使用して行った。 The obtained brick was analyzed for mineral composition, and as physical properties evaluation, apparent porosity and compressive strength were measured, and slag resistance and hot metal resistance were evaluated. The apparent porosity was measured according to JIS-R2205, and the compressive strength was measured according to JIS-R2206. Mineral species were quantified using X-ray diffraction and EPMA.
耐スラグ性及び耐溶銑性については、高炉スラグと銑鉄を誘導加熱溶解して１６００℃に調整した中で試験れんが２０×２０×１８０ｍｍの角棒形状を５ｈ侵食させて侵食厚さを計測し、比較材７である炭素質原料を添加しない窒化アルミニウムボンドアルミナ質れんがの侵食厚さを１００とする侵食損傷指数で評価した。耐溶銑性は溶銑浸漬部の侵食厚さ、耐スラグ性はスラグ−溶銑境界部の最大損耗部の侵食厚さで評価した。侵食損傷指数が小さいほど耐溶銑性及び耐スラグ性に優れるということである。 For slag resistance and hot metal resistance, blast furnace slag and pig iron were induction-heated and melted and adjusted to 1600 ° C, and the erosion thickness was measured by eroding the square shape of a test brick 20 x 20 x 180 mm for 5 h. Evaluation was made with an erosion damage index with the erosion thickness of the aluminum nitride bonded alumina brick to which the carbonaceous raw material as the comparative material 7 was not added being 100. The hot metal resistance was evaluated by the erosion thickness of the hot metal immersion portion, and the slag resistance was evaluated by the erosion thickness of the maximum wear portion of the slag-hot metal interface. The smaller the erosion damage index, the better the hot metal resistance and slag resistance.
また、Ｘ線分析及び顕微鏡観察から実施例１０を除く実施例及び比較例は結合組織に窒化アルミニウムが含まれていることを確認し、実施例１０は結合組織に酸炭化アルミニウムが含まれていることを確認した。 In addition, X-ray analysis and microscopic observation confirmed that Example 10 and Comparative Example other than Example 10 contained aluminum nitride in the connective tissue, and Example 10 contained aluminum oxycarbide in the connective tissue. It was confirmed.
実施例１から実施例４は鱗状黒鉛の添加量が異なる場合の実施例である。鱗状黒鉛を添加していない比較例７と比べると、耐スラグ性が大幅に向上していることがわかる。また耐溶銑性については、比較例４の仮焼無煙炭や比較例５のカーボンブラックと比較して大幅に優れていることもわかる。さらに、鱗状黒鉛を添加しない比較例７と比較しても鱗状黒鉛の添加量が少量であれば、むしろ耐溶銑性が向上する効果も得られている。これは実施例１から実施例４の見掛気孔率が比較例７よりも低いことからして、鱗状黒鉛の添加によって成形性が向上したために組織が緻密になることで耐溶銑性も向上したと推定される。鱗状黒鉛は添加量が増えると耐スラグ性は向上するが耐溶銑性が低下するため、その添加量は４質量％以上１０質量％以下の範囲が好ましいといえる。 Examples 1 to 4 are examples in which the amount of scale-like graphite added is different. It can be seen that the slag resistance is significantly improved as compared with Comparative Example 7 in which no scaly graphite is added. It can also be seen that the hot metal resistance is significantly superior to the calcined anthracite of Comparative Example 4 and the carbon black of Comparative Example 5. Furthermore, even if it compares with the comparative example 7 which does not add scaly graphite, if the addition amount of scaly graphite is small, rather, the effect which hot metal resistance improves will be acquired. This is because the apparent porosity of Example 1 to Example 4 is lower than that of Comparative Example 7, so that the formability is improved by adding scaly graphite, so that the structure becomes dense and the hot metal resistance is also improved. It is estimated to be. As the amount of scaly graphite increases, the slag resistance improves, but the hot metal resistance decreases. Therefore, it can be said that the amount added is preferably in the range of 4 mass% to 10 mass%.
実施例５から実施例７はアルミニウム（Ａｌ）の添加量が異なる場合であるが耐スラグ性及び耐溶銑性ともに優れている。 Examples 5 to 7 are cases where the amount of aluminum (Al) added is different, but both slag resistance and hot metal resistance are excellent.
実施例８及び実施例９は、窒化珪素を添加した例であるが耐スラグ性及び耐溶銑性ともに優れている。 Examples 8 and 9 are examples in which silicon nitride is added, but both slag resistance and hot metal resistance are excellent.
実施例１０は、コークス粒中に埋設して焼成した場合であり、酸炭化アルミニウムが生成しているが、同じアルミニウムの添加量である実施例４と比較して同等の性能を有していることがわかる。 Example 10 is a case where it is embedded in coke grains and fired, and aluminum oxycarbide is produced, but has the same performance as Example 4 which is the same aluminum addition amount. I understand that.
比較例１は、鱗状黒鉛の添加量が３質量％と本発明の下限値を下回るものであるが、耐スラグ性が大幅に低下する結果となった。 In Comparative Example 1, the amount of scaly graphite added was 3% by mass, which was lower than the lower limit of the present invention, but the slag resistance was significantly reduced.
比較例２は、鱗状黒鉛の添加量が１２質量％と本発明の上限値を上回るものであるが、耐溶銑性が大幅に低下している。 In Comparative Example 2, the amount of scaly graphite added is 12% by mass, which exceeds the upper limit of the present invention, but the hot metal resistance is greatly reduced.
比較例３は鱗状黒鉛の粒度が粗いものを使用した場合であるが、同じ添加量で本発明の粒度範囲内の鱗状黒鉛を使用した実施例２と比較すると、耐スラグ性及び耐溶銑性ともに劣ることがわかる。 Comparative Example 3 is a case where scaly graphite having a coarse particle size is used, but both slag resistance and hot metal resistance are compared with Example 2 using scaly graphite within the particle size range of the present invention with the same addition amount. You can see that it is inferior.
比較例４は、仮焼無煙炭を使用した例であるが、同じ量の鱗状黒鉛を添加した実施例２と比較して耐スラグ性及び耐溶銑性ともに劣る。このように、本発明の範囲内では鱗状黒鉛の方が仮焼無煙炭よりも耐溶銑性に優れるという新しい効果を確認した。しかも耐スラグ性も鱗状黒鉛の方が格段に優れる結果となった。 Although the comparative example 4 is an example which uses calcined anthracite, both slag resistance and hot metal resistance are inferior compared with Example 2 which added the same amount of scaly graphite. Thus, within the scope of the present invention, a new effect was confirmed that scaly graphite is superior in hot metal resistance to calcined anthracite. In addition, the slag resistance was significantly better with the scaly graphite.
比較例５は、カーボンブラックを使用した例であるが、同じ量の鱗状黒鉛を添加した実施例２と比較して耐スラグ性及び耐溶銑性ともに大幅に劣る。 Although the comparative example 5 is an example using carbon black, both slag resistance and hot metal resistance are significantly inferior compared with Example 2 which added the same amount of scaly graphite.
比較例６は、Ｓｉ含有量が３．４質量％と本発明の範囲外であり耐溶銑性が不十分である。 In Comparative Example 6, the Si content is 3.4 mass%, which is outside the range of the present invention, and the hot metal resistance is insufficient.
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