JPH0230656A - Magnesia-calcia refractory - Google Patents
Magnesia-calcia refractoryInfo
- Publication number
- JPH0230656A JPH0230656A JP63179368A JP17936888A JPH0230656A JP H0230656 A JPH0230656 A JP H0230656A JP 63179368 A JP63179368 A JP 63179368A JP 17936888 A JP17936888 A JP 17936888A JP H0230656 A JPH0230656 A JP H0230656A
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- magnesia
- calcia
- zirconium silicide
- resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021355 zirconium silicide Inorganic materials 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 7
- 238000004901 spalling Methods 0.000 abstract description 18
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 14
- 229910008257 Zr2Si Inorganic materials 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- -1 Zr2Si Chemical compound 0.000 abstract description 2
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000011819 refractory material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、耐スポーリング性に優れたマグネシア−カル
シア質耐火物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a magnesia-calcia refractory having excellent spalling resistance.
従来技術とその問題点
転炉、製鋼炉、セメントロータリーキルンなどの各種の
炉の内張材としては、ドロマイト質耐火物が広く使用さ
れてきた。しかしながら、近年操業条件の苛酷化、具体
的には、炉の大型化、操業温度の上昇、吹錬時間の短縮
などに伴って、耐スポーリング性、耐熱衝撃性などによ
り優れた耐火物の出現が要求されるようになってきてい
る。Prior art and its problems Dolomite refractories have been widely used as lining materials for various furnaces such as converters, steelmaking furnaces, and cement rotary kilns. However, in recent years, as operating conditions have become more severe, including larger furnaces, higher operating temperatures, and shorter blowing times, refractories with superior spalling resistance and thermal shock resistance have emerged. is increasingly required.
この様な情勢に対応して、例えば、マグネシア原料を主
成分とする塩基性耐火物が開発されている。この耐火物
は、高塩基性スラグに対する耐溶損性には優れているも
のの、熱衝撃に弱い、スラグが浸透し易い、耐火物組織
が変化し易い、構造スポーリングに起因する亀裂により
損傷されるなどの欠点がある。In response to this situation, for example, basic refractories containing magnesia raw materials as a main component have been developed. Although this refractory has excellent erosion resistance against highly basic slag, it is susceptible to thermal shock, is easily penetrated by slag, is susceptible to changes in the refractory structure, and is damaged by cracks caused by structural spalling. There are drawbacks such as.
マグネシア（ＭｇＯ）とカルシア（Ｃａ Ｏ）との併用
により、耐スポーリング性を改善する試みもなされてい
る。この耐火物においては、ＣａＯにより、ＭｇＯの結
晶成長が抑制されて、耐スポーリング性が向上するもの
と期待されている。また、ＣａＯ自身のフラックス化促
進作用により、これが耐火物内に浸透してくるスラグと
反応してスラグを高融点化させ、耐火物内部へのスラグ
浸透を防止する。この場合、耐火物の損傷が、スポーリ
ング律速から溶損律速に変わるので、耐火物の寿命が延
長されるものと有望視されている。Attempts have also been made to improve the spalling resistance by using magnesia (MgO) and calcia (CaO) in combination. In this refractory, CaO suppresses MgO crystal growth and is expected to improve spalling resistance. Further, due to the flux promoting action of CaO itself, it reacts with the slag penetrating into the refractory, increases the melting point of the slag, and prevents the slag from penetrating into the refractory. In this case, damage to the refractory changes from spalling rate-limiting to erosion rate-limiting, so it is expected that the life of the refractory will be extended.
しかしながら、ＣａＯを使用する場合には、耐火物が過
焼結を起こし易く、過焼結を起こした耐火物は、高弾性
体となって、応力に対する変形世が小さくなるため、応
力発生時に変形することなく、亀裂を生じ易くなり、耐
熱スポーリング性が低下する。However, when CaO is used, the refractory is prone to oversintering, and the oversintered refractory becomes a highly elastic body and has a small deformation resistance to stress, so it deforms when stress occurs. Without this, cracks are likely to occur and heat spalling resistance decreases.
問題点を解決するための手段
本発明者は、上記の如き技術の現状に鑑みて種々研究を
重ねた結果、Ｍ ｇ Ｏ−Ｃａ Ｏ系耐火物に特定量の
けい化ジルコニウムを配合することにより、従来技術の
問題点を大巾に軽減し得ることを見出した。Means for Solving the Problems As a result of various studies in view of the current state of the technology as described above, the present inventor has found that by blending a specific amount of zirconium silicide into MgO-CaO-based refractories. It has been found that the problems of the prior art can be greatly alleviated.
すなわち、本発明は、マグネシア２５〜９０重量％とカ
ルシア７５〜１０重量％とからなる耐火骨材１００重量
部にＺｒ２５ｉＳＺｒ３ Ｓｉ２、Ｚｒ５Ｓｉ３および
Ｚｒ５Ｓｉ４からなるけい化ジルコニウムの群から選ば
れた少なくとも一種０．５〜１０重量部を配合したこと
を特徴とするマグネシア−カルシア質耐火物を提供する
ものである。That is, the present invention provides 100 parts by weight of a refractory aggregate consisting of 25-90% by weight of magnesia and 75-10% by weight of calcia, and at least 0.0% of at least one type selected from the group of zirconium silicides consisting of Zr25iSZr3Si2, Zr5Si3 and Zr5Si4. The present invention provides a magnesia-calcia refractory characterized by containing 5 to 10 parts by weight of the magnesia-calcia refractory.
本発明において使用する耐火骨材としては、天然ドロマ
イトクリンカ−１合成ドロマイトクリンカー１焼結マグ
ネシアクリンカ−１電融マグネシアクリンカ−１焼結マ
グライムクリンカー、電融マグライムクリンカーなどが
挙げられる。本発明においては、これら耐火骨材の一種
または二種以上を使用して、Ｍ ｇ ０２５〜９０重量
％（以下単に％とする）とＣａ０７５〜１０％の割合と
なるように調整する。ＭｇＯの割合が２５％未満の場合
には、耐消化性が不十分となるとともに、耐スラグ性が
低下する。一方、ＭｇＯの割合が９０％を上回る場合に
は、耐スポーリング性および耐スラグ溶損性が低下する
。耐火骨材の粒径は、通常５１１１０１以下程度、より
好ましくは３ｍｍ以下程度である。耐火骨材は、必要な
らば、常法にしたがって、粒度調整を行ない、適宜の粒
度分布の配合物として使用することも差し支えない。Examples of the refractory aggregate used in the present invention include natural dolomite clinker-1 synthetic dolomite clinker-1 sintered magnesia clinker-1 fused magnesia clinker-1 sintered magnesia clinker, fused magnesia clinker, and the like. In the present invention, one or more of these refractory aggregates are used to adjust the ratio of M g 025 to 90% by weight (hereinafter simply referred to as %) and Ca 075 to 10%. When the proportion of MgO is less than 25%, the digestion resistance becomes insufficient and the slag resistance decreases. On the other hand, when the proportion of MgO exceeds 90%, the spalling resistance and the slag erosion resistance decrease. The particle size of the refractory aggregate is usually about 511,101 mm or less, more preferably about 3 mm or less. If necessary, the refractory aggregate may be used as a blend having an appropriate particle size distribution by adjusting the particle size according to a conventional method.
本発明で使用するけい化ジルコニウムは、Ｚｒ２ Ｓｉ
、Ｚｒ３ Ｓｉ２、Ｚｒ５ Ｓｉ３およびＺｒ５Ｓｉ４
からなるけい化ジルコニウムの群から選ばれた少なくと
も一種である。これ以外の低融点のけい化ジルコニウム
、例えば、ＺｒＳｉ （融点１５２０℃）、Ｚｒ５ｉ
２（融点１３６０℃）などは、耐火物の使用温度で液相
を形成するので、使用し得ない。けい化ジルコニウムの
粒度は、０．１〜５ａ＋ｍ程度とする。粒子径が０．１
ｍｍ未満の場合には、耐火物使用時にけい化ジルコニウ
ムの粒子内に発生する亀裂が小さくなり、耐熱衝撃性が
十分に発揮されない。また、浸透したスラグとの反応性
が高くなって、浸蝕速度が速くなり、耐蝕性が低下する
。一方、けい化ジルコニウムの粒子径が、５ｍｍを上回
る場合には、耐火物成形時に他の材料粒子とのなじみが
不良となり、成形困難となる。耐火骨材１００重量部（
以下単に部とする）に対するけい化ジルコニウムの配合
量は、０．５〜１０部とする。けい化ジルコニウムの配
合量が、０．５部未満の場合には、耐火物中に発生する
マイクロクラックの量が不十分となって、耐スポーリン
グ性向上の効果が十分に改善されないとともに、浸透し
てきたスラグの高粘性化および高融点化という効果も十
分に発揮されない。一方、けい化ジルコニウムの配合量
が、１０部を上回る場合には、焼結不良による組織の多
孔質化が促進され、耐蝕性が低下する傾向が認められる
。The zirconium silicide used in the present invention is Zr2Si
, Zr3 Si2, Zr5 Si3 and Zr5Si4
At least one member selected from the group of zirconium silicides consisting of Other low melting point zirconium silicides, such as ZrSi (melting point 1520°C), Zr5i
2 (melting point: 1360°C) cannot be used because it forms a liquid phase at the temperature at which the refractory is used. The particle size of zirconium silicide is approximately 0.1 to 5 a+m. Particle size is 0.1
If it is less than mm, the cracks that occur in the particles of zirconium silicide during use as a refractory will become small, and thermal shock resistance will not be sufficiently exhibited. In addition, the reactivity with the penetrated slag increases, the corrosion rate increases, and the corrosion resistance decreases. On the other hand, if the particle size of zirconium silicide exceeds 5 mm, it will not fit well with other material particles during refractory molding, making molding difficult. 100 parts by weight of fireproof aggregate (
The amount of zirconium silicide (hereinafter simply referred to as parts) is 0.5 to 10 parts. If the amount of zirconium silicide is less than 0.5 part, the amount of microcracks generated in the refractory will be insufficient, and the effect of improving spalling resistance will not be sufficiently improved, and the penetration will be reduced. The effects of increasing the viscosity and melting point of the slag, which have been achieved, are not fully demonstrated. On the other hand, when the amount of zirconium silicide exceeds 10 parts, the structure tends to become porous due to poor sintering, and corrosion resistance tends to decrease.
本発明の耐火物は、耐火骨材にけい化ジルコニウム粉末
を配合し、さらに常法に従って、タール、液状フェノー
ル樹脂、ポリプロピレン、ポリウレタン、パラフィン、
ワックスなどの公知の非水系バインダーを添加し、混練
し、成形および焼成することにより得られる。非水系バ
インダーの添加から焼成にいたる工程は、常法どおりな
ので詳述しないが、焼成は、１４００〜１７００℃程度
で行なうことが好ましい。The refractory of the present invention is produced by blending zirconium silicide powder into a refractory aggregate, and further adding tar, liquid phenol resin, polypropylene, polyurethane, paraffin, etc. according to a conventional method.
It is obtained by adding a known non-aqueous binder such as wax, kneading, molding and baking. The steps from addition of the non-aqueous binder to firing are the same as usual and will not be described in detail, but the firing is preferably carried out at about 1400 to 1700°C.
発明の効果 本発明耐火物によれば、以下の如き効果が奏される。Effect of the invention According to the refractory of the present invention, the following effects are achieved.
（１）耐熱スポーリング性に著るしく優れている。(1) Extremely excellent heat spalling resistance.
これは、主に以下の如き理由によるものと推測される。This is presumed to be mainly due to the following reasons.
（イ）けい化ジルコニウム粒子は、焼成時に粒子内に多
数の亀裂を生成する。この亀裂が応力伝播を阻止するの
で、その結果、耐熱スポーリング性が向上する。(a) Zirconium silicide particles generate many cracks within the particles during firing. This crack prevents stress propagation, resulting in improved heat spalling resistance.
（ロ）けい化ジルコニウム粒子（Ｚｒ２Ｓｉを例にとる
）は、焼成時に、下式に示す様に、表面から酸化される
。(b) During firing, zirconium silicide particles (take Zr2Si as an example) are oxidized from the surface as shown in the following formula.
ｚｒ２Ｓ１＋３０２→Ｚｒ０２１１Ｓ１０２＋ＺｒＯ２
この際生ずる体積膨脂により、けい化ジルコニウム粒子
の周囲に亀裂が発生し、上記（イ）の場合と同様に、耐
熱スポーリング性が向上する。zr2S1+302→Zr0211S102+ZrO2
Due to the volume expansion that occurs at this time, cracks are generated around the zirconium silicide particles, and as in the case (a) above, the heat spalling resistance is improved.
（２）耐構造スポーリング性にも著しく優れている。す
なわち、けい化ジルコニウムが、使用時に耐火物内に浸
透してくるスラグと反応して、これを高融点化および高
粘性化させるので、スラグのそれ以上の浸透を抑制し、
耐構造スポーリング性を向上させるのである。(2) It also has excellent structural spalling resistance. In other words, zirconium silicide reacts with the slag that permeates into the refractory during use, increasing the melting point and increasing the viscosity of the refractory, thereby suppressing further permeation of the slag.
This improves structural spalling resistance.
実施例
以下に実施例および比較例を示し、本発明の特徴とする
ところをより一層明確にする。EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.
実施例１
第１表に示す割合（重量部）で各原料を配合し、バイン
ダーとしてポリウレタン２重世部を加えて混練し、ＪＩ
Ｓ並形れんが形状に成形し、１６５０℃で焼成して、本
発明耐火物を得た。Example 1 Each raw material was blended in the proportions (parts by weight) shown in Table 1, and 2 parts of polyurethane was added as a binder and kneaded.
The refractories of the present invention were obtained by molding into the shape of S-sized bricks and firing at 1650°C.
得られた耐火物の各種の物性を下記の方法により測定し
た。Various physical properties of the obtained refractory were measured by the following methods.
■、気孔率・・・ＪＩＳ Ｒ２２０５■、嵩比重・・
・ＪＩＳ Ｒ２２０５■、圧縮強さ・・・ＪＩＳ
Ｒ２２０６■１曲げ強さく１４００℃）・・・ＪＩＳ
Ｒ２２０６また、得られた耐火物を電気炉内に挿入し
、１２００℃で１５分間保持→空冷１５分間からなる加
熱およ゛び冷却サイクルを繰返し、耐火物に剥落が認め
られるまでの回数を調べて、耐スポーリング性を判定し
た。■, Porosity...JIS R2205■, Bulk specific gravity...
・JIS R2205■, compressive strength...JIS
R2206■1 Bending strength 1400℃)...JIS
R2206 In addition, the obtained refractory was inserted into an electric furnace, and the heating and cooling cycle consisting of holding at 1200°C for 15 minutes → air cooling for 15 minutes was repeated, and the number of times until flaking was observed in the refractory was determined. The spalling resistance was determined.
さらに、ＣａＯ／５ｉ０２比＝２のスラグを使用して、
得られた耐火物を１７００℃で８時間のロータリースラ
グテストに供し、比較例品の侵蝕量を１００として、相
対的侵蝕量を測定した。Furthermore, using a slag with a CaO/5i02 ratio of 2,
The obtained refractories were subjected to a rotary slag test at 1700° C. for 8 hours, and the relative amount of corrosion was measured, setting the amount of corrosion of the comparative example product as 100.
これらの結果を第２表に示す。These results are shown in Table 2.
第２表に示す結果から、本発明による耐火物が、優れた
耐熱スポーリング性および耐構造スポーリング性（耐ス
ラグ性）を備えていることが、明らかである。From the results shown in Table 2, it is clear that the refractory according to the present invention has excellent heat spalling resistance and structural spalling resistance (slag resistance).
（以上）(that's all)
Claims (1)
０重量％とからなる耐火骨材１００重量部にＺｒ＿２Ｓ
ｉ、Ｚｒ＿３Ｓｉ＿２、Ｚｒ＿５Ｓｉ＿３およびＺｒ＿
５Ｓｉ＿４からなるけい化ジルコニウムの群から選ばれ
た少なくとも一種０．５〜１０重量部を配合したことを
特徴とするマグネシア−カルシア質耐火物。(1) 25-90% by weight of magnesia and 75-1% by weight of calcia
Zr_2S is added to 100 parts by weight of fireproof aggregate consisting of 0% by weight.
i, Zr_3Si_2, Zr_5Si_3 and Zr_
A magnesia-calcia refractory comprising 0.5 to 10 parts by weight of at least one selected from the group of zirconium silicides consisting of 5Si_4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63179368A JPH0230656A (en) | 1988-07-18 | 1988-07-18 | Magnesia-calcia refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63179368A JPH0230656A (en) | 1988-07-18 | 1988-07-18 | Magnesia-calcia refractory |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0230656A true JPH0230656A (en) | 1990-02-01 |
Family
ID=16064633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63179368A Pending JPH0230656A (en) | 1988-07-18 | 1988-07-18 | Magnesia-calcia refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230656A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002020425A1 (en) * | 2000-09-08 | 2002-03-14 | Forschungszentrum Karlsrube Gmbh | Moulding compound, use thereof and a method for producing an oxide-ceramic sintered body |
| CN115322001A (en) * | 2022-09-15 | 2022-11-11 | 江阴誉球耐火材料有限公司 | High-temperature-resistant iron runner castable and preparation method thereof |
-
1988
- 1988-07-18 JP JP63179368A patent/JPH0230656A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002020425A1 (en) * | 2000-09-08 | 2002-03-14 | Forschungszentrum Karlsrube Gmbh | Moulding compound, use thereof and a method for producing an oxide-ceramic sintered body |
| US7208037B2 (en) | 2000-09-08 | 2007-04-24 | Forschungszentrum Karlsruhe, Gmbh | Molding compound, use thereof and a method for producing an oxide-ceramic sintered body |
| CN115322001A (en) * | 2022-09-15 | 2022-11-11 | 江阴誉球耐火材料有限公司 | High-temperature-resistant iron runner castable and preparation method thereof |
| CN115322001B (en) * | 2022-09-15 | 2023-07-07 | 江阴誉球耐火材料有限公司 | High-temperature-resistant iron runner castable and preparation method thereof |
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