WO2016208666A1 - 溶銑製造炉の炉床用れんが - Google Patents

溶銑製造炉の炉床用れんが Download PDF

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WO2016208666A1
WO2016208666A1 PCT/JP2016/068641 JP2016068641W WO2016208666A1 WO 2016208666 A1 WO2016208666 A1 WO 2016208666A1 JP 2016068641 W JP2016068641 W JP 2016068641W WO 2016208666 A1 WO2016208666 A1 WO 2016208666A1
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sialon
mass
aln
brick
hot metal
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PCT/JP2016/068641
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English (en)
French (fr)
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三島　昌昭
倫路 中込
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黒崎播磨株式会社
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Priority to JP2017524964A priority Critical patent/JP6412646B2/ja
Priority to EP16814435.0A priority patent/EP3315475B1/en
Publication of WO2016208666A1 publication Critical patent/WO2016208666A1/ja

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    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
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    • F27D1/0003—Linings or walls
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
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Definitions

  • the present invention relates to a hearth brick for a hot metal production furnace for producing hot metal such as a blast furnace or a smelting reduction furnace.
  • the hearth of a hot metal production furnace for producing hot metal such as a blast furnace or a smelting reduction furnace is mainly made of carbonaceous brick with aggregate of graphite or alumina brick with aggregate of alumina.
  • One of the factors governing the service life is wear of these hearth bricks.
  • carbonaceous bricks are the mainstream as the lining material for the blast furnace hearth side walls, but bricks with a high carbon content tend to melt into the hot metal when used in the blast furnace hearth.
  • the hot metal resistance 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.
  • 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.
  • sialon bonded alumina bricks containing ⁇ '-sialon represented by the chemical formula Si 6-Z Al Z O Z N 8-Z in the matrix portion contain almost no carbon, so they have excellent hot metal resistance and are also suitable for use in blast furnaces.
  • sialon bond alumina bricks have higher strength at high temperatures and higher resistance to alkali erosion than conventional oxide bricks, and are typically silicon carbide bond bricks and nitriding bricks having a non-oxide bond structure. It is suitable as lining for blast furnace hearth because it has low thermal conductivity compared to silicon-bonded brick and is strong against structural spalling.
  • Patent Document 1 the matrix portion (bound substrate), Z value (refers to a Z value in ⁇ '- sialon of formula Si 6-Z Al Z O Z N 8-Z. Hereinafter the same.) 0
  • a sialon bonded alumina brick containing 12 to 45% by weight of 5 to 4 ⁇ ′-sialon is disclosed.
  • the Si in ⁇ ′-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.
  • H in Table 3 of Patent Document 2 discloses a sialon bond alumina brick containing 20% by mass of 15R type as an AlN polymorphic sialon and further containing 8% by mass of TiN, and sialon (sialon) and In comparison, it is described that not only the resistance to corrosion by steel but also the bending strength of the substance is improved.
  • the present inventors investigated the hot metal resistance of the sialon bond alumina brick manufactured according to H in Table 3 of Patent Document 2 it was almost the same level as the conventional sialon bond alumina brick. It was found that the hot metal resistance needs to be further improved for application as a hearth brick.
  • Patent Document 3 the brick structure is composed of a crystalline phase and an amorphous phase.
  • the crystalline phase is 80 to 98% by mass of corundum, and 1 to 18% by mass of aluminum nitride and aluminum carbonate crystals.
  • Blast furnace hearth bricks having an amorphous phase of 0.5 to 10% by mass and a Si content of 3% by mass or less are disclosed.
  • the brick for blast furnace hearth of Patent Document 3 is excellent in hot metal resistance because of low content of Si, but aluminum nitride is easily hydrated and inferior in hydration resistance, so that during brick storage, construction or after construction Hydration may cause generation of harmful gases and deterioration of brick tissue.
  • JP-T 6-502140 Patent No. 3212600
  • Patent No. 3212600 Japanese National Patent Publication No. 10-509686 International Publication No. 2009/72652
  • the problem to be solved by the present invention is to provide a hearth brick for a hot metal production furnace having improved hot metal resistance without reducing slag resistance and hydration resistance.
  • Si has the property of being easily dissolved in hot metal. Therefore, in order to improve the hot metal resistance of bricks, the present inventors have made alumina with a low Si content in ⁇ ′-sialon, that is, ⁇ ′-sialon having a large Z value, or AlN polymorphic sialon. Focused on brick.
  • the mineral composition is corundum: 40 to 95% by mass, one or more AlN polymorphic sialon selected from 2H ⁇ type, 27R type and 21R type: 5 to 60% by mass and AlN: 5 And consisting of Si 3 N 4 : 3 mass% or less (including 0), And the brick for a hearth of a hot metal manufacturing furnace which contains the said AlN polymorphic sialon 5 mass% or more in a matrix part.
  • AlN polymorphic sialon selected from corundum: 40 to 94% by mass, graphite and / or coke: 10% by mass or less, 2H ⁇ type, 27R type and 21R type : 5 to 59% by mass or less, AlN: 5% by mass or less (including 0), and Si 3 N 4 : 3% by mass or less (including 0), And the brick for a hearth of a hot metal manufacturing furnace which contains the said AlN polymorphic sialon 5 mass% or more in a matrix part. (3) The brick for the hearth of the hot metal production furnace according to (1) or (2), wherein the matrix part contains 10 to 25% by mass of the AlN polymorphic sialon and 5 to 30% by mass of corundum.
  • the AlN polymorphic sialon is a Si—Al—O—N solid solution, and in the Ramsdell notation, the 2H ⁇ type, 27R type, 21R type, 12H type, 15R type and 8H type in ascending order of Si content.
  • the 2H ⁇ type, 27R type, 21R type, 12H type, 15R type and 8H type in ascending order of Si content.
  • 3 types of 2H ⁇ type, 27R type and 21R type having a low Si content are used.
  • the tissue of the brick according to the present invention is composed of an aggregate part made of aggregate and a matrix part which is a connective tissue that connects the aggregates.
  • the aggregate is a particle that keeps the original shape of the refractory particles used as a raw material, and the matrix portion is formed by sintering the used raw material fine particles so that the aggregate and the aggregate are aggregated. It is a continuous piece of tissue that exists between them.
  • the brick of the present invention has a corundum content of 40 to 95% by mass (40 to 94% by mass in the case of containing graphite and / or coke), preferably 55 to 80% by mass in order to utilize the excellent hot metal resistance by corundum. contains. If the amount is less than 40% by mass, the hot metal resistance becomes insufficient. If the amount exceeds 95% by mass, the three types of AlN polymorphic sialon are relatively reduced. Therefore, the effect of improving the slag resistance by the AlN polymorphic sialon cannot be obtained. , Slag resistance decreases.
  • the three types of AlN polymorphic sialon are contained in the matrix part in an amount of 5% by mass or more in total of one or more of them.
  • the conventional sialon bond alumina can be obtained by adding 5% by mass or more to the matrix portion.
  • the hot metal resistance can be enhanced particularly in the matrix portion containing sialon bonds, and at the same time, the effect of suppressing the penetration of hot metal can be enhanced.
  • the three types of AlN polymorphic sialons may be contained in the aggregate part, and 5 to 60% by mass (5 to 59% by mass in the case of containing graphite and / or coke), preferably 15% together with the matrix part. -40% by mass is contained. If it is less than 5% by mass, the effect of improving the slag resistance inherent to sialon is insufficient, and if it exceeds 60% by mass, the corundum is relatively reduced, so that the hot metal resistance is insufficient.
  • the brick of the present invention can contain graphite and / or coke at 10% by mass or less in order to further improve the slag resistance.
  • the amount exceeds 10% by mass the above-mentioned problem caused by bricks with a large amount of carbon components occurs, that is, the problem that carbon melts into hot metal during use in the hearth and lowers the hot metal resistance.
  • the brick of the present invention contains 5-30% by mass of corundum in the matrix portion, thereby improving the hot metal resistance, and in addition, the total of one or more of the above three types of AlN polymorphic sialon is 10 to 10%. By containing 30% by mass, it is possible to make a brick that simultaneously improves the hot metal resistance and slag resistance.
  • the brick of the present invention does not contain the above three types of AlN polymorphic sialon in the aggregate part, and the brick part is further improved in hot metal resistance by using only the corundum that is difficult to dissolve in the hot metal. It can also be.
  • AlN is contained in an amount of less than 5% by mass, it does not cause a problem due to a decrease in hydration resistance, but rather can improve the hot metal resistance.
  • the crystal size of the three types of AlN polymorphic sialon in the brick of the present invention a finer one is more suitable for practical use because it tends to form a dense brick structure and exhibits high strength.
  • at least the crystal size of the AlN polymorphic sialon in the matrix portion is preferably 0.5 mm or less, more preferably 0.05 mm or less.
  • the brick of the present invention is excellent in hot metal resistance and hydration resistance, the life of the hearth of a hot metal production furnace such as a blast furnace or a smelting reduction furnace can be improved.
  • the brick of the present invention is a conventional sialon bond alumina brick manufacturing method, the composition of the desired AlN polymorphic sialon after nitriding firing (the above three types of compositions) and the ratio so that the content thereof becomes an ultrafine alumina powder, It can be obtained by using a refractory raw material composition containing Al powder and Si powder, adding a binder, kneading, and firing at 1000 to 1450 ° C. in a nitrogen atmosphere after molding. That is, by this production method, the brick of the present invention containing one of the three types of target AlN polymorphic sialon in the matrix portion can be obtained.
  • the AlN polymorphic sialon aggregate is superalumina so as to have the composition of the target AlN polymorphic sialon (the above three types of composition). It can be obtained by sizing a sintered aggregate obtained by firing a raw material mixture in which the amount of fine powder, Al fine powder and Si fine powder is adjusted at 800 to 1450 ° C. in a nitrogen atmosphere. By adding this aggregate to the above-mentioned refractory raw material composition, the brick of the present invention containing the above-mentioned three kinds of AlN polymorphic sialon is also obtained in the aggregate part. And when using the refractory raw material compound which added the some AlN polymorphic sialon aggregate from which said kind differs among said 3 types, this invention contains 2 or 3 types of AlN polymorphic sialon among said 3 types. You can get goodwill.
  • alumina having an average particle size of 50 ⁇ m or less specifically, activated alumina (calcined alumina) as the ultrafine alumina powder.
  • activated alumina calcined alumina
  • electrofused alumina or sintered alumina it is difficult to produce the three types of AlN polymorphic sialon.
  • the crystal size of the AlN polymorphic sialon can be controlled by the size of the fine powder used as a raw material and the maximum temperature and holding time of the nitriding firing conditions.
  • the particle size of the ultrafine alumina powder used as a raw material is 50 ⁇ m or less
  • the particle size of Al powder and Si powder is 0.1 mm or less
  • the maximum temperature of nitriding firing conditions is 1400 ° C. and held for about 10 hours good.
  • the three kinds of AlN polymorphic sialon are contained in the matrix of the present invention.
  • brick can be obtained, AlN and Si 3 N 4 may be produced in small amounts due to slight excess or deficiency of the raw materials used.
  • AlN is 5% by mass or less
  • Si 3 N 4 is 3% by mass or less, and more preferably 1% by mass or less, it can be allowed without adverse effects.
  • only one of the three types of AlN polymorphic sialon is generated in the matrix portion.
  • the above-mentioned AlN polymorphic sialon aggregate is pulverized into a fine powder and added to the refractory raw material composition.
  • the corundum contained in the brick of the present invention can be fused alumina and sintered alumina as raw materials, and the graphite can be scaled graphite, soil graphite, electrode scraps, and the like. And in order to make these contain in an aggregate, the raw material of a particle size of 0.1 mm or more can be used.
  • Patent Document 2 describes that the addition of TiN to sialon bond bricks improves the corrosion resistance against steel, but TiN has a property of dissolving into hot metal, and voids generated by this dissolution. In order to accelerate the wear of the hot metal, the brick of the present invention is not included.
  • Table 1 shows examples of the brick of the present invention together with comparative examples.
  • the bricks in each example were kneaded by adding an appropriate amount of a resol-type phenol resin to the refractory raw material composition shown in Table 1, and after forming a JIS ordinary brick-shaped molded body with an oil press, heat-treated at 250 ° C And fired at 1400 ° C. in a nitrogen atmosphere.
  • the resulting brick was analyzed for mineral composition, and as a physical property evaluation, bulk specific gravity, apparent porosity, compressive strength, and bending strength at 1200 ° C. were measured, and further erosion resistance (slag resistance and hot metal resistance). Property) and hydration resistance.
  • the amount of aggregate in the brick tissue was evaluated using commercially available image analysis software from an image of the brick cut surface.
  • the amount of sialon contained in the matrix was determined from the nitrogen content in the brick and the identification of the sialon phase by X-ray diffraction.
  • the crystal size of sialon contained in the matrix part was measured from a microscopic image obtained by an electron microscope.
  • the amount of mineral components other than sialon contained in the matrix portion was measured using an X-ray diffraction method, a chemical analysis method, and a wavelength dispersion X-ray analyzer, respectively.
  • blast furnace slag and pig iron were induction-heated and melted and adjusted to 1600 ° C., and the test brick 20 ⁇ 20 ⁇ 180 mm square bar shape was eroded for 5 hours to measure the erosion thickness.
  • the erosion damage index was evaluated with an erosion thickness of 100.
  • the hot metal resistance was evaluated by the erosion thickness of the hot metal immersion part, and the slag resistance was evaluated by the erosion thickness of the maximum wear part of the slag-hot metal interface.
  • the amount of ammonia gas generated in a state where a JIS ordinary test brick was immersed in room temperature water for 24 hours was measured with an ammonia concentration meter, and the ammonia gas amount of Comparative Example 4 was expressed as an index. The smaller the index, the better the hydration resistance.
  • Example 1 is a 2H ⁇ type AlN polymorphic sialon
  • Example 2 is a 27R type AlN polymorphic sialon
  • Example 3 is a brick of the present invention containing 20R% of 21R type AlN polymorphic sialon in the matrix part. These are much more resistant to hot metal than bricks containing 20% by mass of the 12H type AlN polymorphic sialon of Comparative Example 1, 15R type AlN polymorphic sialon of Comparative Example 2, and ⁇ sialon of Comparative Example 3 in the matrix part, respectively. It is understood that is superior.
  • the brick which contains 11 mass% of AlN of the comparative example 4 in a matrix is excellent in hot metal resistance, it turns out that the hydration resistance is falling.
  • Examples 4 to 7 are different in the content of AlN polymorphic sialon and corundum in the matrix within the scope of the present invention, and are all excellent in hot metal resistance, slag resistance and hydration resistance.
  • Example 8 contains AlN polymorph sialon in the aggregate part and the matrix part, and is excellent in all of hot metal resistance, slag resistance and hydration resistance.
  • Example 9 contains scaly graphite as graphite in the aggregate part, and is particularly excellent in slag resistance.
  • the matrix portion is composed only of AlN polymorphic sialon, and all of the hot metal resistance, slag resistance and hydration resistance are excellent.
  • Example 11 contains 5% by mass of AlN and Si 3 N 4 in total, but there is no significant adverse effect on hot metal resistance, slag resistance and hydration resistance.
  • Comparative Example 5 and Comparative Example 6 the content of AlN polymorphic sialon exceeds the upper limit of the present invention. Since corundum is relatively reduced, the effect of improving the hot metal resistance by corundum is reduced.
  • Comparative Example 7 is such that the content of AlN polymorphic sialon is below the lower limit of the present invention. Although the hot metal resistance is well maintained by corundum, the effect of improving slag resistance by sialon is diminished.

Abstract

本発明は、耐溶銑性及び耐水和性に優れる溶銑製造炉の炉床用れんがを提供する。本発明の溶銑製造炉の炉床用れんがは、鉱物組成が、コランダム：４０～９５質量％と、２Ｈδ型、２７Ｒ型及び２１Ｒ型から選択した１種又は２種以上のＡｌＮ多形サイアロン：５～６０質量％以下と、ＡｌＮ：５質量％以下（０を含む）と、Ｓｉ３Ｎ４：３質量％以下（０を含む）とからなり、しかもマトリックス部に、前記ＡｌＮ多形サイアロンを５質量％以上含有する。

Description

溶銑製造炉の炉床用れんが
　本発明は、高炉や溶融還元炉などの溶銑を製造する溶銑製造炉の炉床用れんがに関する。
　高炉や溶融還元炉などの溶銑を製造する溶銑製造炉の炉床には、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ところ、炉寿命を支配する要因の１つとしてこれらの炉床用れんがの損耗が挙げられる。
　例えば高炉の炉床部側壁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。
　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。また、サイアロンボンドアルミナれんがは、従来の酸化物系れんがと比較して高温強度が高くてアルカリ侵食に対する抵抗性も高く、非酸化物系結合組織を有するれんがとして代表的な炭化珪素結合れんが及び窒化珪素結合れんがと比較して低熱伝導性であり、更に構造的スポーリングにも強い点から、高炉炉床部用の内張りれんがとして適している。
　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。
　また、特許文献２の表３のＨには、ＡｌＮ多形サイアロンとして１５Ｒ型を２０質量％含有し、しかもＴｉＮを８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おり、シアロン（サイアロン）と比較してスチールによる腐食に対する耐性のみならず、物質の曲げ強度を向上させることが記載されている。しかし本発明者らが、この特許文献２の表３のＨに従って製造したサイアロンボンドアルミナれんがについて、耐溶銑性を調査したところ、従来のサイアロンボンドアルミナれんがとほぼ同等レベルであり、溶銑製造炉の炉床用れんがとして適用するには、更に耐溶銑性の改善の必要があることがわかった。
　一方、特許文献３には、れんがの組織が結晶相と非晶質相とからなり、結晶相が、コランダムが８０～９８質量％、並びに窒化アルミニウム及び炭酸化アルミニウム結晶が１～１８質量であり、非晶質相が０．５～１０質量％であり、且つ、Ｓｉ含有量が３質量％以下である高炉炉床用れんがが開示されている。この特許文献３の高炉炉床用れんがは、Ｓｉの含有量が少ないため耐溶銑性に優れるが、窒化アルミニウムは水和しやすく耐水和性に劣るため、れんがの保存中、施工中あるいは施工後に水和により有害ガス発生やれんが組織の劣化が生じることがある。
特表平６－５０２１４０号公報（特許第３２１２６００号公報） 特表平１０－５０９６８６号公報 国際公開第２００９／７２６５２号
　本発明が解決しようとする課題は、耐スラグ性及び耐水和性を低下させることなく、耐溶銑性を向上させた溶銑製造炉の炉床用れんがを提供することにある。
　サイアロンを構成するＳｉ、Ａｌ、Ｏ、及びＮの４成分において、Ｓｉは溶銑に溶解しやすい性質を有する。そこで本発明者らは、れんがの耐溶銑性を高めるために、β’－サイアロンの中でＳｉ含有率の少ない、すなわちＺ値の大きなβ’－サイアロン、あるいはＡｌＮ多形サイアロンを含有するアルミナ質れんがに着目した。そして、Ｓｉ、Ａｌ、Ｏ、及びＮの４成分で構成されるサイアロン相の耐溶銑性、耐スラグ性及び耐水和性について検討したところ、ＡｌＮ多形サイアロンの中で２Ｈδ型、２７Ｒ型及び２１Ｒ型の３種のＡｌＮ多形サイアロンが、格段に耐溶銑性に優れており、耐スラグ性及び耐水和性も低下しないことを見出した。
　すなわち、本発明によれば、次の（１）から（５）の溶銑製造炉の炉床用れんがが提唱される。
（１）鉱物組成が、コランダム：４０～９５質量％と、２Ｈδ型、２７Ｒ型及び２１Ｒ型から選択した１種又は２種以上のＡｌＮ多形サイアロン：５～６０質量％以下と、ＡｌＮ：５質量％以下（０を含む）と、Ｓｉ３Ｎ４：３質量％以下（０を含む）とからなり、
　しかもマトリックス部に、前記ＡｌＮ多形サイアロンを５質量％以上含有する、溶銑製造炉の炉床用れんが。
（２）鉱物組成が、コランダム：４０～９４質量％と、黒鉛及び／又はコークス：１０質量％以下と、２Ｈδ型、２７Ｒ型及び２１Ｒ型から選択した１種又は２種以上のＡｌＮ多形サイアロン：５～５９質量％以下と、ＡｌＮ：５質量％以下（０を含む）と、Ｓｉ３Ｎ４：３質量％以下（０を含む）とからなり、
　しかもマトリックス部に、前記ＡｌＮ多形サイアロンを５質量％以上含有する、溶銑製造炉の炉床用れんが。
（３）マトリックス部に、前記ＡｌＮ多形サイアロンを１０～２５質量％、及びコランダムを５～３０質量％含有する、（１）又は（２）に記載の溶銑製造炉の炉床用れんが。
（４）骨材部に、前記ＡｌＮ多形サイアロンを含有しない、（１）から（３）のいずれかに記載の溶銑製造炉の炉床用れんが。
（５）前記ＡｌＮ多形サイアロンの結晶サイズが０．５ｍｍ以下である、（１）から（４）のいずれかに記載の溶銑製造炉の炉床用れんが。
　ここで、ＡｌＮ多形サイアロンとはＳｉ－Ａｌ－Ｏ－Ｎ固溶体であって、Ｒａｍｓｄｅｌｌの表記法において、Ｓｉ含有率の少ない順に２Ｈδ型、２７Ｒ型、２１Ｒ型、１２Ｈ型、１５Ｒ型及び８Ｈ型の６種があるが、本発明ではこのうち、Ｓｉ含有率の少ない２Ｈδ型、２７Ｒ型及び２１Ｒ型の３種を使用する。
　本発明のれんがの組織は骨材からなる骨材部と、その骨材どうし結合する結合組織であるマトリックス部とからなる。そして図１に示すように、骨材とは原料として使用した耐火物粒子の原形をほぼ保った粒子であり、マトリックス部とは使用した原料微粒子どうしが焼結することで骨材と骨材の間に存在する連続した組織の部分である。
　本発明のれんがは、コランダムによる優れた耐溶銑性を利用するためにコランダムを４０～９５質量％（黒鉛及び／又はコークスを含有する場合は４０～９４質量％）、好ましくは５５～８０質量％含有する。４０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前記３種のＡｌＮ多形サイアロンが少なくなるため、これらＡｌＮ多形サイアロンによる耐スラグ性向上効果が得られず、耐スラグ性が低下する。
　本発明のれんがにおいて前記３種のＡｌＮ多形サイアロンは、その１種又は２種以上の合計で、マトリックス部に５質量％以上含有させる。前述のとおり前記３種のＡｌＮ多形サイアロンは、β’－サイアロン等のほかのサイアロンに比べ耐溶銑性に優れるから、これをマトリックス部に５質量％以上含有させることで、従来のサイアロンボンドアルミナれんがと比較して、特にサイアロンボンドを含むマトリックス部において耐溶銑性を高めることができ、同時に溶銑の浸透抑制効果を高めることができる。
　前記３種のＡｌＮ多形サイアロンは骨材部に含有させてもよく、マトリックス部と合せて５～６０質量％（黒鉛及び／又はコークスを含有する場合は５～５９質量％）、好ましくは１５～４０質量％含有させる。５質量％未満ではサイアロンが本来有する耐スラグ性の向上効果が不十分となり、６０質量％を超えると相対的にコランダムが少なくなるため耐溶銑性が不足する。
　また、本発明のれんがは、その耐スラグ性を更に高めるために黒鉛及び／又はコークスを１０質量％以下で含有することができる。１０質量％を超えると炭素成分の多いれんがで生じる前述の問題点、すなわち炉床部での使用時に炭素が溶銑中へ溶け出し耐溶銑性が低下するという問題が生じる。
　更に、本発明のれんがは、そのマトリックス部にコランダムを５～３０質量％含有することで耐溶銑性を高め、しかも前記３種のＡｌＮ多形サイアロンの１種又は２種以上を合計で１０～３０質量％含有することで、耐溶銑性と耐スラグ性を同時に高めたれんがとすることもできる。
　また、本発明のれんがは、その骨材部に前記３種のＡｌＮ多形サイアロンを含有せず、当該骨材部を溶銑に溶けにくいコランダムのみとすることで、更に耐溶銑性を高めたれんがとすることもできる。
　本発明のれんがにおいて、ＡｌＮは５質量％未満であれば含有しても耐水和性の低下に伴う不具合が生じることはなく、むしろ耐溶銑性を高めることもできる。
　本発明のれんが中の前記３種のＡｌＮ多形サイアロンの結晶サイズは、細かい方が緻密なれんが組織を形成しやすく、高強度を示すことから実用上は好適である。具体的には、少なくともマトリックス部中のＡｌＮ多形サイアロンの結晶サイズは０．５ｍｍ以下が好ましく、より好ましくは０．０５ｍｍ以下である。
　本発明のれんがは、耐溶銑性及び耐水和性に優れるため、高炉や溶融還元炉などの溶銑製造炉の炉床部の寿命を向上させることができる。
本発明のれんがの組織写真の一例である。
　本発明のれんがは、従来のサイアロンボンドアルミナれんがの製法において、窒化焼成後に目的とするＡｌＮ多形サイアロンの組成（前記３種の組成）とその含有量になるような比率で、アルミナ超微粉、Ａｌ粉末及びＳｉ粉末を含有する耐火原料配合物を使用し、バインダーを添加して混練し、成形後に窒素雰囲気下で１０００～１４５０℃で焼成することで得ることができる。すなわち、この製法により、目的とする前記３種のＡｌＮ多形サイアロンのうちの１種をマトリックス部に含有する本発明のれんがを得ることができる。例えば、２７Ｒ型のＡｌＮ多形サイアロンを生成し含有させるには、耐火原料配合物の各原料の配合をＡｌ：Ｓｉ：Ａｌ２Ｏ３＝６５～６６：２～１０：２４～３３にすれば良い。
　一方、骨材部に前記３種のＡｌＮ多形サイアロンを含有させる場合、そのＡｌＮ多形サイアロン骨材は、目的とするＡｌＮ多形サイアロンの組成（前記３種の組成）になるようにアルミナ超微粉とＡｌ微粉とＳｉ微粉の量を調整した原料混合物を窒素雰囲気下で８００～１４５０℃で焼成した焼結骨材を整粒して得ることができる。この骨材を前述の耐火原料配合物に添加することで骨材部にも前記３種のＡｌＮ多形サイアロンを含有する本発明のれんがが得られる。そして、前記３種のうちで種類が異なる複数のＡｌＮ多形サイアロン骨材を添加した耐火原料配合物を使用すると、前記３種のうち２種又は３種のＡｌＮ多形サイアロンを含有する本発明のれんがを得ることができる。
　前記の製法において、アルミナ超微粉としては、平均粒径が５０μｍ以下のアルミナを使用し、具体的には活性アルミナ（仮焼アルミナ）を使用することが好ましい。電融アルミナや焼結アルミナを使用した場合、前記３種のＡｌＮ多形サイアロンの生成が困難となる。そして、ＡｌＮ多形サイアロンの結晶サイズは、原料として使用する微粉の大きさや窒化焼成条件の最高温度と保持時間によって制御することが可能で、例えば結晶サイズが０．５ｍｍ以下のＡｌＮ多形サイアロンにするためには、原料として使用するアルミナ超微粉の粒径を５０μｍ以下、並びにＡｌ粉末及びＳｉ粉末の粒度は０．１ｍｍ以下とし、窒化焼成条件の最高温度を１４００℃として１０時間程度保持すれば良い。
　このように、原料としてアルミナ超微粉、Ａｌ粉末、及びＳｉ粉末を所定の比率で含有する耐火原料配合物を使用することで、前記３種のＡｌＮ多形サイアロンがマトリックス中に含まれる本発明のれんがが得られるが、使用する原料の若干の過不足により、ＡｌＮとＳｉ３Ｎ４が少量生成することがある。しかし、ＡｌＮは５質量％以下、Ｓｉ３Ｎ４は３質量％以下、より好ましくはそれぞれ１質量％以下であれば、悪影響なく許容することができる。なお、このとき、マトリックス部には、前記３種のＡｌＮ多形サイアロンのうちいずれか１種のみ生成する。したがって、マトリックス部に複数種のＡｌＮ多形サイアロンを含有させたい場合には、前記のＡｌＮ多形サイアロン骨材を粉砕して微粉としたものを耐火原料配合物に添加する。
　また、本発明のれんがに含まれるコランダムは原料として電融アルミナ及び焼結アルミナなどを、黒鉛は鱗状黒鉛、土壌黒鉛、及び電極屑などを使用することができる。そして、これらを骨材に含有させるためには０．１ｍｍ以上の粒度の原料を使用することができる。
　なお、前述のとおり特許文献２には、サイアロンボンドれんがにＴｉＮを添加するとスチールに対する耐食性が向上することが記載されているが、ＴｉＮは溶銑中へ溶解する性質があり、この溶解で発生した空隙に溶銑が浸透しれんがの損耗を促進するため、本発明のれんがには含有させない。
　表１に本発明のれんがの実施例を比較例とともに示す。
Figure JPOXMLDOC01-appb-T000001
　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、窒素雰囲気下１４００℃で焼成して得た。
　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、かさ比重、見掛け気孔率、圧縮強さ、及び１２００℃での曲げ強さを測定し、更に耐侵食性（耐スラグ性及び耐溶銑性）と耐水和性を評価した。
　鉱物組成の分析において、れんが組織中の骨材の量はれんが切断面を撮影した画像から市販の画像解析ソフトを使って評価した。マトリックス部に含まれるサイアロンの量はれんが中の窒素含有率とＸ線回折法によるサイアロン相の同定とから決定した。マトリックス部に含まれるサイアロンの結晶サイズは電子顕微鏡による顕微鏡像から計測した。マトリックス部に含まれるサイアロン以外の鉱物成分の量はＸ線回折法と化学分析法と波長分散型Ｘ線分析器を利用してそれぞれ測定した。
　かさ比重と見掛け気孔率はＪＩＳ－Ｒ２２０５、圧縮強さはＪＩＳ－Ｒ２２０６、１２００℃での曲げ強さはＪＩＳ－Ｒ２２１３に従い測定した。
　耐侵食性については、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、比較例３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。
　耐水和性については、ＪＩＳ並形の試験れんがを常温水中に２４時間浸漬した状態で発生するアンモニアガス量をアンモニア濃度計で測定し、比較例４のアンモニアガス量を１００として指数で表示した。この指数が小さいほど耐水和性に優れるということである。
　実施例１は２Ｈδ型ＡｌＮ多形サイアロン、実施例２は２７Ｒ型ＡｌＮ多形サイアロン、実施例３は２１Ｒ型ＡｌＮ多形サイアロンをマトリックス部にそれぞれ２０質量％含有する本発明のれんがである。これらは、比較例１の１２Ｈ型ＡｌＮ多形サイアロン、比較例２の１５Ｒ型ＡｌＮ多形サイアロン、比較例３のβサイアロンをマトリックス部にそれぞれ２０質量％含有するれんがと比較すると格段に耐溶銑性が優れていることがわかる。また、比較例４のＡｌＮをマトリックスに１１質量％含有するれんがは耐溶銑性に優れるが、耐水和性が低下していることがわかる。
　実施例４から実施例７は本発明の範囲内で、マトリックス中のＡｌＮ多形サイアロン及びコランダムの含有量が異なるもので、いずれも耐溶銑性、耐スラグ性及び耐水和性に優れる。
　実施例８は骨材部とマトリックス部とにＡｌＮ多形サイアロンを含有するもので、耐溶銑性、耐スラグ性及び耐水和性のいずれも優れる。
　実施例９は、骨材部に黒鉛として鱗状黒鉛を含有するもので、とりわけ耐スラグ性に優れる。
　実施例１０は、マトリックス部がＡｌＮ多形サイアロンのみで構成されるもので、耐溶銑性、耐スラグ性及び耐水和性のいずれも優れる。
　実施例１１は、ＡｌＮとＳｉ３Ｎ４を合計で５質量％含有するものであるが、耐溶銑性、耐スラグ性及び耐水和性に大きな悪影響はない。
　一方、比較例５と比較例６はＡｌＮ多形サイアロンの含有量が本発明の上限を超えるものである。コランダムが相対的に少なくなったことにより、コランダムによる耐溶銑性の向上効果が減退している。
　比較例７はＡｌＮ多形サイアロンの含有量が本発明の下限を下回るものである。耐溶銑性はコランダムにより良好に維持されているが、サイアロンによる耐スラグ性の向上効果が減退している。

Claims (5)

  1. 　鉱物組成が、コランダム：４０～９５質量％と、２Ｈδ型、２７Ｒ型及び２１Ｒ型から選択した１種又は２種以上のＡｌＮ多形サイアロン：５～６０質量％以下と、ＡｌＮ：５質量％以下（０を含む）と、Ｓｉ３Ｎ４：３質量％以下（０を含む）とからなり、
    　しかもマトリックス部に、前記ＡｌＮ多形サイアロンを５質量％以上含有する、溶銑製造炉の炉床用れんが。
  2. 　鉱物組成が、コランダム：４０～９４質量％と、黒鉛及び／又はコークス：１０質量％以下と、２Ｈδ型、２７Ｒ型及び２１Ｒ型から選択した１種又は２種以上のＡｌＮ多形サイアロン：５～５９質量％以下と、ＡｌＮ：５質量％以下（０を含む）と、Ｓｉ３Ｎ４：３質量％以下（０を含む）とからなり、
    　しかもマトリックス部に、前記ＡｌＮ多形サイアロンを５質量％以上含有する、溶銑製造炉の炉床用れんが。
  3. 　マトリックス部に、前記ＡｌＮ多形サイアロンを１０～２５質量％、及びコランダムを５～３０質量％含有する、請求項１又は請求項２に記載の溶銑製造炉の炉床用れんが。
  4. 　骨材部に、前記ＡｌＮ多形サイアロンを含有しない、請求項１から請求項３のいずれかに記載の溶銑製造炉の炉床用れんが。
  5. 　前記ＡｌＮ多形サイアロンの結晶サイズが０．５ｍｍ以下である、請求項１から請求項４のいずれかに記載の溶銑製造炉の炉床用れんが。
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