JP6215111B2 - Alumina-silica brick for blast furnace hot air tube or lining of hot air furnace - Google Patents
Alumina-silica brick for blast furnace hot air tube or lining of hot air furnace Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 37
- 239000011449 brick Substances 0.000 title claims description 36
- 239000000377 silicon dioxide Substances 0.000 title claims 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 description 46
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 43
- 239000011707 mineral Substances 0.000 claims description 43
- 229910052851 sillimanite Inorganic materials 0.000 claims description 35
- 238000010304 firing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- 230000035939 shock Effects 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 229910052849 andalusite Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 6
- 239000011819 refractory material Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910052850 kyanite Inorganic materials 0.000 description 5
- 239000010443 kyanite Substances 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- -1 chamotte Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000011451 fired brick Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Compositions Of Oxide Ceramics (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Description
本発明は高炉熱風管設備、特に環状管及び熱風本管、熱風炉の連絡管、混合室、又はバーナーダクト部などに内張り耐火物として使用されるアルミナ−シリカ系れんがに関する。 The present invention relates to blast furnace hot air tube equipment, and more particularly to an alumina-silica brick used as a lining refractory for an annular tube and a hot air main tube, a hot air furnace connecting tube, a mixing chamber, or a burner duct.
高炉熱風管あるいは熱風炉の内張り耐火物は耐熱衝撃性と耐クリープ性が要求されるため、一般的にアルミナ−シリカ系れんがが使用されている。特に近年は、熱風炉で高温熱風を発生する操業へ移りつつあり、内張り耐火物としてはより高い耐クリープ性と耐熱衝撃性が要求されるようになってきている。 Since the blast furnace blast furnace or the refractory lining the hot blast furnace is required to have thermal shock resistance and creep resistance, generally, an alumina-silica brick is used. In particular, in recent years, the operation has been shifted to an operation for generating high-temperature hot air in a hot stove, and higher creep resistance and thermal shock resistance have been demanded as lining refractories.
従来、アルミナ−シリカ系れんがとしては、特許文献１に、コランダム、ムライト、シリマナイト、アンダルサイト、シャモット、珪石のうち１種又は２種類以上の耐火原料と粘土とを組み合わせて得られる、化学成分がＳｉＯ２：３０〜１０ｗｔ％、Ａｌ２Ｏ３：６５〜８０ｗｔ％のアルミナ−シリカ系れんがが開示されている。 Conventionally, as an alumina-silica-based brick, there is a chemical component obtained by combining Patent Document 1 with one or more refractory raw materials and clay among corundum, mullite, sillimanite, andalusite, chamotte, and silica. SiO 2: 30~10wt%, Al 2 O 3: 65~80wt% alumina - silica brick is disclosed.
また、特許文献２には、コランダム・シリマナイト質原料１０〜４０ｗｔ％、アンダルサイト４０〜７５ｗｔ％、ろう石３〜４０ｗｔ％、粘土２〜１０ｗｔ％よりなる配合物を混練、成形後、１０００℃以上で焼成してなり、かつ、化学成分がＡｌ２Ｏ３：３５〜７０ｗｔ％、ＳｉＯ２：２５〜６０ｗｔ％、残部：７ｗｔ％以下のアルミナ−シリカ系れんがが開示されている。 Patent Document 2 discloses that a composition comprising 10 to 40 wt% corundum and sillimanite raw material, 40 to 75 wt% andalusite, 3 to 40 wt% wax, and 2 to 10 wt% clay is kneaded and molded at 1000 ° C. or higher. in baked becomes in and chemical composition Al 2 O 3: 35~70wt%, SiO 2: 25~60wt%, the balance: 7 wt% or less of the alumina - silica brick is disclosed.
高炉熱風管及び熱風炉の連絡管、混合室又はバーナーダクト部などの内張り耐火物は、高炉の操業過程で１０００℃以上の高温熱風と１００℃前後の低温熱風とに長期間繰り返し晒される。したがって、これらの内張り耐火物には長期間の使用において耐クリープ性と耐熱衝撃性とが要請される。これらを両立できれば、炉寿命の延長及び熱風炉の高温操業化が図れることでエネルギー効率も向上することが期待できる。 Lined refractories such as blast furnace hot air tubes and hot air furnace connection tubes, mixing chambers or burner ducts are repeatedly exposed to high temperature hot air of 1000 ° C. or higher and low temperature hot air of around 100 ° C. for a long time during the operation of the blast furnace. Therefore, these lining refractories are required to have creep resistance and thermal shock resistance in long-term use. If both of these can be achieved, it is expected that the energy efficiency can be improved by extending the life of the furnace and increasing the temperature of the hot stove.
上述の特許文献１及び特許文献２に開示されているアルミナ−シリカ系れんがは、高炉の熱風管や熱風炉の内張り耐火物として使用するには耐クリープ性あるいは耐熱衝撃性が不十分という問題がある。また、一般に、耐クリープ性を向上しようとすると耐熱衝撃性が低下する問題もある。 The alumina-silica bricks disclosed in Patent Document 1 and Patent Document 2 described above have a problem of insufficient creep resistance or thermal shock resistance for use as a blast furnace hot-air tube or a hot-blast furnace lining refractory. is there. In general, there is a problem that the thermal shock resistance is lowered when an attempt is made to improve creep resistance.
そこで、本発明が解決しようとする課題は、高炉熱風管及び熱風炉の内張り耐火物に要請される耐熱衝撃性と耐クリープ性に優れたアルミナ−シリカ系れんがを提供することにある。 Therefore, the problem to be solved by the present invention is to provide an alumina-silica brick excellent in thermal shock resistance and creep resistance required for blast furnace hot air tubes and lining refractories of hot air furnaces.
本発明の一観点によれば、電融アルミナを３８質量％以上７０質量％以下、シリマナイト族鉱物を２０質量％以上５０質量％以下含有し、かつ、電融アルミナとシリマナイト族鉱物との合量が７５質量％以上９５質量％以下で、残部が電融アルミナ及びシリマナイト族鉱物以外のアルミナ系原料、シリカ系原料及びアルミナ−シリカ系原料のうちの１種以上からなる配合物を、混練し、成形後、焼成して得られたれんがであって、該れんが中のシリマナイト族鉱物の残存率が９０質量％以上である、高炉熱風管又は熱風炉の内張り用アルミナ−シリカ系れんがが提供される。 According to one aspect of the present invention, the amount of fused alumina is 38% by mass or more and 70% by mass or less, and the amount of silimanite group mineral is 20% by mass or more and 50% by mass or less. Knead a mixture of 75 mass% or more and 95 mass% or less, with the balance being one or more of alumina-based materials other than fused alumina and silimanite group minerals, silica-based materials, and alumina-silica-based materials, Provided is an alumina-silica-based brick for blast furnace hot-air tube or hot-blast furnace lining, which is a brick obtained by firing after molding and having a residual ratio of silimanite group mineral in the brick of 90% by mass or more. .
本発明によれば、原料配合物として電融アルミナとシリマナイト族鉱物とを組み合わせて配合したことで、高炉熱風管及び熱風炉用として優れた耐熱衝撃性と耐クリープ性とを両立したアルミナ−シリカ系れんが得ることができる。したがって、高炉熱風管及び熱風炉の長寿命化を図ることができる。また、熱風炉の操業条件を高温へ移行できることでエネルギー効率が向上し、地球環境負荷の低減に寄与することができる。 According to the present invention, alumina-silica having both excellent thermal shock resistance and creep resistance for blast furnace hot air tubes and hot air furnaces by combining electrofused alumina and silimanite group minerals as a raw material composition. A system brick can be obtained. Therefore, the lifetime of the blast furnace hot blast tube and the hot blast furnace can be extended. Moreover, energy efficiency improves by being able to transfer the operating conditions of a hot stove to high temperature, and it can contribute to reduction of a global environmental load.
本発明のアルミナ−シリカ系れんがは、その原料配合物として電融アルミナとシリマナイト族鉱物とを組み合わせて配合することに特徴がある。電融アルミナは耐クリープ性に優れる原料であるが、熱膨張率が大きいため耐熱衝撃性に劣る問題がある。また、シリマナイト族鉱物の熱膨張率は更に大きい。具体的には、電融アルミナの熱膨張率は１０００℃で０．６〜０．８％であり、シリマナイト族鉱物の熱膨張率は１０００℃で０．８〜１．３％である。 The alumina-silica brick of the present invention is characterized in that it is blended in combination with a fused alumina and a sillimanite group mineral as a raw material blend. Electrofused alumina is a raw material with excellent creep resistance, but has a problem of poor thermal shock resistance due to its high coefficient of thermal expansion. Further, the thermal expansion coefficient of the sillimanite group mineral is even greater. Specifically, the thermal expansion coefficient of fused alumina is 0.6 to 0.8% at 1000 ° C., and the thermal expansion coefficient of sillimanite group mineral is 0.8 to 1.3% at 1000 ° C.
しかし、本発明者らは、これらの原料を使用した配合物を成形して焼成すると、焼成中に電融アルミナとシリマナイト族鉱物との熱膨張差に起因する微小な隙間がれんが組織内に発生し、この微小な隙間によって弾性率が低下するとともに亀裂進展が阻止されるために、耐熱衝撃性に優れるれんがとなり、更に、電融アルミナ本来の耐クリープ性に優れる特性も維持されることから、耐熱衝撃性と耐クリープ性を両立したれんがが得られることを知見した。 However, when the present inventors molded and fired a blend using these raw materials, a minute gap due to the difference in thermal expansion between the fused alumina and the sillimanite group mineral occurs in the structure during firing. However, since the elastic modulus is reduced by this minute gap and crack growth is prevented, it becomes a brick with excellent thermal shock resistance, and furthermore, the characteristics excellent in the creep resistance inherent in fused alumina are maintained. It was found that bricks with both thermal shock resistance and creep resistance can be obtained.
電融アルミナは３８質量％以上７０質量％以下で使用する。３８質量％未満では耐クリープ性が不十分となり、７０質量％を超えると耐熱衝撃性が低下する。電融アルミナは焼結アルミナと比較して、その粒子をコランダム結晶の集合体であると考えたとき、電融アルミナの結晶粒界は焼結アルミナのそれに比較して少ない。その結果、高温での機械的特性、例えば強度、クリープ抵抗性などに差が生じてくる。このことから、本発明では電融アルミナを使用する。電融アルミナとしては、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特に問題なく使用することができる。Ａｌ２Ｏ３含有量としては９５質量％以上のものが好ましい。 Electrofused alumina is used at 38 mass% or more and 70 mass% or less. If it is less than 38% by mass, the creep resistance becomes insufficient, and if it exceeds 70% by mass, the thermal shock resistance is lowered. Compared with sintered alumina, fused alumina has fewer crystal grain boundaries than fused alumina when it is considered that the particles are aggregates of corundum crystals. As a result, differences occur in mechanical properties at high temperatures, such as strength and creep resistance. For this reason, electrofused alumina is used in the present invention. Any electrofused alumina can be used as long as it is used as a raw material for ordinary refractories. The Al 2 O 3 content is preferably 95% by mass or more.
シリマナイト族鉱物は２０質量％以上５０質量％以下で使用する。２０質量％未満では耐熱衝撃性が不十分となり、５０質量％を超えると耐クリープ性が低下する。本発明で使用するシリマナイト族鉱物は、シリマナイト、アンダルサイト及びカイアナイトのうち１種又は２種以上を組み合わせて使用することができる。これらのシリマナイト族鉱物の熱膨張率はいずれも電融アルミナのそれより大きいので、電融アルミナとシリマナイト族鉱物とを組み合わせて配合することにより得られる耐熱衝撃性向上という特徴は、シリマナイト族鉱物が１種の場合はもちろん、２種以上を組み合わせても同様に得られる。これらの原料は、天然から採掘される鉱物であり、それらを精製して使用することができる。より耐クリープ性を確保したい場合には、不純物としての酸化鉄が約２質量％以下、好ましくは１質量％以下とすることもできる。 The sillimanite group mineral is used in an amount of 20% by mass to 50% by mass. If it is less than 20% by mass, the thermal shock resistance is insufficient, and if it exceeds 50% by mass, the creep resistance is lowered. The sillimanite group mineral used in the present invention can be used alone or in combination of two or more of sillimanite, andalusite, and kyanite. The thermal expansion coefficient of these sillimanite group minerals is greater than that of fused alumina, so the characteristic of improved thermal shock resistance obtained by combining fused alumina and sillimanite group minerals is that In the case of one type, of course, it can be similarly obtained by combining two or more types. These raw materials are minerals mined from nature and can be used by refining them. When it is desired to further secure creep resistance, the iron oxide as an impurity can be about 2% by mass or less, preferably 1% by mass or less.
電融アルミナとシリマナイト族鉱物との合量は７５質量％以上９５質量％以下とする。７５質量％未満では耐クリープ性及び耐熱衝撃性を満足できず、９５質量％を超えると強度が不十分になる。 The total amount of the fused alumina and the silimanite group mineral is 75% by mass or more and 95% by mass or less. If it is less than 75% by mass, the creep resistance and the thermal shock resistance cannot be satisfied, and if it exceeds 95% by mass, the strength becomes insufficient.
残部は、電融アルミナ及びシリマナイト族鉱物以外のアルミナ系原料、シリカ系原料及びアルミナ−シリカ系原料のうちの１種以上とする。すなわち、残部の量は５質量％以上２５質量％以下である。残部を構成するアルミナ系原料としては仮焼アルミナなどの活性アルミナの他に焼結アルミナなど、シリカ系原料としては 石英、トリジマイト、クリストバライトなどからなる結晶性シリカの他に非晶質のシリカガラスなど、アルミナ−シリカ系原料としては、粘土、ムライトなどが使用できる。例えば、残部としては仮焼アルミナと粘土を合量で２質量％以上１５質量％以下で使用することもできる。仮焼アルミナと粘土は、焼結助剤として強度向上効果がある。 The balance is one or more of alumina-based materials, silica-based materials, and alumina-silica-based materials other than fused alumina and sillimanite group minerals. That is, the remaining amount is 5% by mass or more and 25% by mass or less. The remaining alumina-based material includes sintered alumina in addition to activated alumina such as calcined alumina, and the silica-based material includes amorphous silica glass in addition to crystalline silica made of quartz, tridymite, cristobalite, etc. As the alumina-silica-based material, clay, mullite and the like can be used. For example, as the balance, calcined alumina and clay can be used in a total amount of 2% by mass to 15% by mass. Calcinated alumina and clay have a strength improving effect as a sintering aid.
本発明のアルミナ−シリカ系れんがは、上述の配合物を、混練し、成形後、焼成する通常の方法によって得られる。 The alumina-silica brick of the present invention can be obtained by an ordinary method of kneading, molding and firing the above-mentioned blend.
そして、本発明のアルミナ−シリカ系れんがは、焼成後のれんが中のシリマナイト族鉱物の残存率を９０％質量以上とすることでより耐熱衝撃性を向上させることができる。ここで、焼成後のれんが中のシリマナイト族鉱物の残存率とは[１００×（焼成後のれんが中のシリマナイト族鉱物の割合（質量％）／配合物中のシリマナイト族鉱物の割合（質量％））]（質量％）である。 And the alumina-silica-type brick of this invention can improve a thermal shock resistance more by making the residual rate of the sillimanite group mineral in the brick after baking into 90% mass or more. Here, the residual ratio of the silimanite group mineral in the brick after firing is [100 × (the proportion of the silimanite group mineral in the brick after firing (mass%) / the proportion of the silimanite group mineral in the blend (mass%). )] (Mass%).
その理由は次のとおりである。シリマナイト族鉱物は、高温になると鉱物組成がムライトとクリストバライトに変化する。本発明によるれんがの耐熱衝撃性と耐クリープ性の両立には電融アルミナとシリマナイト族鉱物との熱膨張差に起因する微小な隙間がれんが組織内に発生することが必須である。焼成過程でシリマナイト族鉱物がムライトとクリストバライトへ変化すると、前述のれんが組織内に発生する微小な隙間が不足して本発明による効果が不十分となる。したがって、焼成後のれんが中にシリマナイト族鉱物をある程度含有する状態で焼成することで更に耐熱衝撃性が向上する。この焼成後のれんが中のシリナマイト族鉱物の残存率を焼成温度の指標とすることで、より正確にれんが組成を制御することができる。そして、数回シリマナイト族鉱物の残存率を測定した後は、焼成温度でシリマナイト族鉱物の残存率を管理することができる。例えば、１６００℃以下で焼成することでシリマナイト族鉱物の残存率を９０質量％以上とすることができる。なお、焼成温度の下限は、焼成が実現できる限り制限はないが、一般的には１０００℃程度である。 The reason is as follows. Silimanite group minerals change to mullite and cristobalite at high temperatures. In order to achieve both the thermal shock resistance and the creep resistance of the brick according to the present invention, it is essential that a minute gap due to the difference in thermal expansion between the fused alumina and the silimanite group mineral is generated in the brick. When the sillimanite group mineral is changed to mullite and cristobalite in the firing process, the above-mentioned bricks are not sufficiently formed in the structure and the effect of the present invention becomes insufficient. Therefore, the thermal shock resistance is further improved by firing in a state in which the fired brick contains some silimanite group mineral. By using the residual rate of the silinamite group mineral in the brick after firing as an index of the firing temperature, the brick composition can be controlled more accurately. And after measuring the residual rate of a sillimanite group mineral several times, the residual rate of a sillimanite group mineral can be managed with a calcination temperature. For example, the residual rate of the sillimanite group mineral can be 90% by mass or more by firing at 1600 ° C. or less. The lower limit of the firing temperature is not limited as long as firing can be realized, but is generally about 1000 ° C.
他の観点からいうと、焼成後のれんが中のシリマナイト族鉱物のＸ線最強回折強度が５００ｃｐｓ以上となるように焼成することで耐熱衝撃性が向上する。ここで、天然産シリマナイト族鉱物としてはアンダルサイト、カイアナイト、シリマナイトの３種類があり、これらのＸ線最強回折面は、アンダルサイトが（１１０）、カイアナイトが（０−２１）、シリマナイトが（２１０）である。本発明でいうシリマナイト族鉱物のＸ線最強回折強度は、シリマナイト、アンダルサイト、カイアナイトそれぞれのＸ線最強回折面から生じる回折強度の和である。なお、コランダムのＸ線最強回折面は（１０４）である。 From another viewpoint, the thermal shock resistance is improved by firing so that the X-ray strongest diffraction intensity of the sillimanite group mineral in the brick after firing becomes 500 cps or more. Here, there are three kinds of natural sillimanite group minerals, andalusite, kyanite, and sillimanite, and these X-ray strongest diffraction planes are (110) for andalusite, (0-21) for kyanite, and (210) for sillimanite. ). The X-ray strongest diffraction intensity of the sillimanite group mineral referred to in the present invention is the sum of diffraction intensities generated from the X-ray strongest diffraction surfaces of sillimanite, andalusite, and kyanite. The corundum X-ray strongest diffraction surface is (104).
本発明のアルミナ−シリカ系れんがは、高炉熱風管又は熱風炉の連絡管、混合室、バーナーダクト部などの内張り耐火物として使用することで高炉熱風管及び熱風炉の寿命を延長することができる。更に、熱風炉の操業条件を高温へ移行できることでエネルギー効率が向上し、地球環境負荷の低減に寄与できる。 The alumina-silica-based brick of the present invention can extend the life of blast furnace hot air tubes and hot air furnaces when used as lining refractories such as blast furnace hot air tubes or hot air furnace connecting tubes, mixing chambers, and burner ducts. . Furthermore, energy efficiency is improved because the operating conditions of the hot stove can be shifted to high temperatures, which can contribute to reduction of the global environmental load.
本発明の実施例と比較例とを表１及び表２に示す。 Examples and comparative examples of the present invention are shown in Tables 1 and 2.
表１及び表２に示す配合物に水系のバインダーを添加して混練し、プレス機で２３０ｍｍ×１１５ｍｍ×７５ｍｍのれんがを成形し、乾燥後、１５００℃で焼成してアルミナ−シリカ系れんがを得た。なお、実施例１３は１５５０℃、実施例１４は１６００℃、比較例９は１６４０℃、比較例１０は１６８０℃で焼成したものである。 A water-based binder is added to the formulations shown in Tables 1 and 2 and kneaded. A 230 mm × 115 mm × 75 mm brick is formed with a press, dried, and fired at 1500 ° C. to obtain an alumina-silica brick. It was. Note that Example 13 was fired at 1550 ° C., Example 14 at 1600 ° C., Comparative Example 9 at 1640 ° C., and Comparative Example 10 at 1680 ° C.
配合物には、電融アルミナはＡｌ２Ｏ３含有量が９９．５質量％のものを、粘土はＡｌ２Ｏ３含有量が４０質量％のものを、仮焼アルミナはＡｌ２Ｏ３含有量が９９．０質量％のものを使用した。また、シリマナイト族鉱物としてアンダルサイトは、Ａｌ２Ｏ３含有量が６０質量％、ＳｉＯ２含有量が３７質量％のものを、カイアナイトはＡｌ２Ｏ３含有量が５８質量％、ＳｉＯ２含有量が３９質量％のものを、シリマナイトはＡｌ２Ｏ３含有量が７５質量％、ＳｉＯ２含有量が２０質量％のものを使用した。 In the blend, fused alumina has an Al 2 O 3 content of 99.5% by mass, clay has an Al 2 O 3 content of 40% by mass, and calcined alumina contains Al 2 O 3 An amount of 99.0% by mass was used. Further, as the sillimanite group mineral, andalusite has an Al 2 O 3 content of 60% by mass and SiO 2 content of 37% by mass, and kyanite has an Al 2 O 3 content of 58% by mass and SiO 2 content. There those 39 wt%, sillimanite is Al 2 O 3 content 75 wt%, SiO 2 content was used in 20 mass%.
得られたアルミナ−シリカ系れんがについて、表１及び表２に結果を示すように、Ｘ線最強回折強度、かさ比重、見掛け気孔率、圧縮強さ、クリープ、荷重軟化点及び耐熱衝撃性を測定した。 As shown in Tables 1 and 2, the obtained alumina-silica brick was measured for X-ray strongest diffraction intensity, bulk specific gravity, apparent porosity, compressive strength, creep, load softening point, and thermal shock resistance. did.
れんが中あるいは配合物中のシリマナイト族鉱物の割合（質量％）は内標準物質としてシリコンを使用した内部標準法によりＸ線最強回折強度から求めた。なお、内部標準法とは、内部標準物質と試料を一定の割合で混合し、成分濃度と回折線強度比との間には直線比例関係が得られることを利用して、濃度が既知の標準試料で検量線を作成し分析する公知の方法である。 The ratio (mass%) of the silimanite group mineral in the brick or the blend was determined from the X-ray strongest diffraction intensity by an internal standard method using silicon as an internal standard substance. In addition, the internal standard method is a standard whose concentration is known by using the fact that the internal standard substance and the sample are mixed at a certain ratio and a linear proportional relationship is obtained between the component concentration and the diffraction line intensity ratio. This is a known method for preparing and analyzing a calibration curve with a sample.
Ｘ線最強回折強度とは、粉末Ｘ線解析法で得られたそれぞれの鉱物の回折パターンにおいて最も強い回折ピークの強度（ｃｐｓ）である。本実施例では、加速電圧が４５ｋＶ、電流２００ｍＡで発生したＸ線をφ１０ｍｍの円盤面に照射したときに生じる回折Ｘ線をスキャンスピード８．０ｄｅｇ／ｍｉｎの条件で測定した。 The X-ray strongest diffraction intensity is the intensity (cps) of the strongest diffraction peak in the diffraction pattern of each mineral obtained by the powder X-ray analysis method. In this example, diffracted X-rays generated when an X-ray generated at an acceleration voltage of 45 kV and a current of 200 mA was irradiated onto a disk surface of φ10 mm were measured under a scan speed of 8.0 deg / min.
かさ比重と見掛け気孔率はＪＩＳ−Ｒ２２０５、圧縮強さはＪＩＳ−Ｒ２２０６に従い測定した。クリープはＪＩＳ−Ｒ２６５８に従い１５５０℃で５時間、０．２ＭＰａの条件で測定した。荷重軟化点はＪＩＳ−Ｒ２２０９に従い０．２ＭＰａの条件で測定した。耐熱衝撃性はＪＩＳ−Ｒ２６５７に従い８００℃加熱後の水冷法により、剥落発生までの回数を測定した。 Bulk specific gravity and apparent porosity were measured according to JIS-R2205, and compressive strength was measured according to JIS-R2206. Creep was measured in accordance with JIS-R2658 at 1550 ° C. for 5 hours at 0.2 MPa. The load softening point was measured under the condition of 0.2 MPa according to JIS-R2209. For thermal shock resistance, the number of times until peeling occurred was measured by a water cooling method after heating at 800 ° C. in accordance with JIS-R2657.
実施例１から実施例５は、配合物中の電融アルミナとアンダルサイトとの含有量が異なる例であるが、いずれも本発明の範囲内であり耐熱衝撃性及び耐クリープ性に優れている。 Examples 1 to 5 are examples in which the contents of the fused alumina and the andalusite in the blend are different, but both are within the scope of the present invention and are excellent in thermal shock resistance and creep resistance. .
実施例６は、電融アルミナとアンダルサイト以外に、焼結アルミナとシャモットを使用した例、実施例７は仮焼アルミナに代えて焼結アルミナを使用した例であるが、いずれも本発明の範囲内であり耐熱衝撃性及び耐クリープ性に優れている。 Example 6 is an example using sintered alumina and chamotte in addition to electrofused alumina and andalusite, and Example 7 is an example using sintered alumina instead of calcined alumina. It is within the range and has excellent thermal shock resistance and creep resistance.
実施例８〜実施例１２は、種々のシリマナイト族鉱物を使用した例であるが、いずれも本発明の範囲内であり耐熱衝撃性及び耐クリープ性に優れる。 Examples 8 to 12 are examples using various sillimanite group minerals, all of which are within the scope of the present invention and are excellent in thermal shock resistance and creep resistance.
比較例１は、電融アルミナとシリマナイト族鉱物の合量が９７質量％と本発明の上限を超えており、強度低下が著しく、耐熱衝撃性も劣ることから実用上問題となる。 Comparative Example 1 is practically problematic because the total amount of fused alumina and silimanite group mineral is 97% by mass, exceeding the upper limit of the present invention, the strength is significantly reduced, and the thermal shock resistance is inferior.
比較例２は、電融アルミナとシリマナイト族鉱物の合量が７０質量％と本発明の下限を下回っており、耐熱衝撃性と耐クリープ性が実用上問題となる。 In Comparative Example 2, the total amount of fused alumina and sillimanite group mineral is 70 mass%, which is lower than the lower limit of the present invention, and thermal shock resistance and creep resistance are practically problematic.
比較例３は、電融アルミナが３０質量％と本発明の下限を下回っており、耐熱衝撃性は優れるが耐クリープ性が実用上問題となる。 In Comparative Example 3, the fused alumina is 30% by mass, which is below the lower limit of the present invention, and the thermal shock resistance is excellent, but the creep resistance becomes a practical problem.
比較例４は、電融アルミナが８０質量％と本発明の上限を超えており、耐熱衝撃性が劣っている。 In Comparative Example 4, the fused alumina is 80% by mass, exceeding the upper limit of the present invention, and the thermal shock resistance is inferior.
比較例５は、シリマナイト族鉱物が５５質量％と本発明の上限を超えており、耐熱衝撃性は優れるが耐クリープ性が実用上問題となる。 In Comparative Example 5, 55% by mass of the sillimanite group mineral exceeds the upper limit of the present invention, and the thermal shock resistance is excellent, but creep resistance becomes a practical problem.
比較例６は、シリマナイト族鉱物が１５質量％と本発明の下限を下回っており、耐クリープ性は優れるが耐熱衝撃性が実用上問題となる。 In Comparative Example 6, the sillimanite group mineral is 15 mass%, which is lower than the lower limit of the present invention, and the creep resistance is excellent, but the thermal shock resistance is a practical problem.
比較例７は、シリマナイト族鉱物を使用せず、代わりにムライトを使用したものである。耐クリープ性は良好であるものの、低強度であり、耐熱衝撃性が実用上問題となる。 In Comparative Example 7, no sillimanite group mineral was used, and mullite was used instead. Although the creep resistance is good, the strength is low and the thermal shock resistance is a problem in practice.
比較例８は、電融アルミナの代わりに焼結アルミナを使用したものであるが、耐クリープ性が実用上問題となる。 In Comparative Example 8, sintered alumina is used instead of fused alumina, but creep resistance becomes a practical problem.
実施例１３は１５５０℃、実施例１４は１６００℃で焼成したものであり、シリマナイトの残存率はそれぞれ９５質量％及び９０質量％と本発明の範囲内であるが、比較例９は焼成温度が１６４０℃と高いためシリマナイトの残存率は８５質量％と本発明の下限値を下回った。その結果、耐熱衝撃性が低下する結果となった。 Example 13 was calcined at 1550 ° C. and Example 14 was calcined at 1600 ° C., and the remaining ratio of sillimanite was 95% by mass and 90% by mass, respectively, within the scope of the present invention. Since it was as high as 1640 ° C., the residual rate of sillimanite was 85% by mass, which was lower than the lower limit of the present invention. As a result, the thermal shock resistance was lowered.
比較例１０は焼成温度が１６８０℃でありシリマナイト残存率が６０質量％と本発明の下限値を下回った。その結果、耐熱衝撃性が更に低下する結果となった。 In Comparative Example 10, the firing temperature was 1680 ° C., and the sillimanite residual rate was 60% by mass, which was lower than the lower limit of the present invention. As a result, the thermal shock resistance was further reduced.
本発明の実施例１のれんがを熱風炉の混合室の内張りれんがとして使用した結果、操業から５年経過後もれんがの脱落、損傷等の不具合は発生せず、順調に稼働中である。 As a result of using the brick of Example 1 of the present invention as the lining brick of the mixing chamber of the hot stove, after 5 years from the operation, there are no problems such as falling off or damage of the brick, and it is operating smoothly.
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