JP2702510B2 - Preparation method of raw materials for carbon-containing refractories - Google Patents
Preparation method of raw materials for carbon-containing refractoriesInfo
- Publication number
- JP2702510B2 JP2702510B2 JP63174302A JP17430288A JP2702510B2 JP 2702510 B2 JP2702510 B2 JP 2702510B2 JP 63174302 A JP63174302 A JP 63174302A JP 17430288 A JP17430288 A JP 17430288A JP 2702510 B2 JP2702510 B2 JP 2702510B2
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- Prior art keywords
- carbon
- metal
- present
- weight
- pitch
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- Carbon And Carbon Compounds (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、例えば金属溶融容器の内張り用耐火物とし
て使用されるカーボン含有耐火物の製造に使用する造粒
子に関する。Description: TECHNICAL FIELD The present invention relates to granules used for producing carbon-containing refractories used, for example, as refractories for lining metal melting vessels.
金属溶融容器の内張り用耐火物は、近年操業条件の苛
酷化に伴い耐食性，耐スポール性に優れたカーボンを含
む材料が開発され、耐用性の向上に大きく寄与してい
る。As refractories for lining metal melting containers, carbon-containing materials having excellent corrosion resistance and spall resistance have been developed in recent years as operating conditions have become severer, and have greatly contributed to improving durability.
このような耐火物のカーボン源としては、定形耐火物
においては、鱗状黒鉛が一般的であるが、流動性を付与
するために水を使用する不定形耐火物においては、鱗状
黒鉛の使用によって添加水分の増加を招き、多量に使用
することは不可能である。そのためピッチのように耐酸
化性に劣るカーボンを、それも少量しか使用できないの
が現状である。この点から耐火物に配合されるカーボン
の酸化防止が材料の特性改善の重要なポイントとなる。As a carbon source of such a refractory, in the case of a fixed refractory, scaly graphite is generally used.However, in the case of an amorphous refractory in which water is used to impart fluidity, it is added by the use of scaly graphite. It causes an increase in moisture and cannot be used in large quantities. Therefore, at present, only a small amount of carbon having poor oxidation resistance, such as pitch, can be used. From this point, prevention of oxidation of carbon compounded in the refractory is an important point for improving the characteristics of the material.
カーボン含有耐火物の耐酸化性，耐食性の改善と熱間
強度の向上のために、金属アルミニウムのような低融点
金属を添加することが、例えば特開昭55−107749号公報
に記載されているように公知である。Japanese Patent Application Laid-Open No. 55-107749 discloses the addition of a low-melting-point metal such as metallic aluminum in order to improve the oxidation resistance and corrosion resistance of carbon-containing refractories and the hot strength. It is known as such.
しかし、キャスタブルのように水を使用する不定形耐
火材料においては、金属アルミニウムは常温で水和反応
を生じ、金属添加による効果を消失してしまうばかりで
なく、むしろ水和反応時に多量の水素ガスを発生し、こ
れによって組織劣化を招く問題がある。However, in amorphous refractory materials that use water, such as castables, metallic aluminum causes a hydration reaction at room temperature, not only losing the effect of adding metal, but also a large amount of hydrogen gas during the hydration reaction. This causes a problem of causing tissue deterioration.
この添加金属の水和反応を抑制する方法として樹脂と
金属を加熱混合して金属に被覆処理を施し、金属表面に
疎水性を付与し、水和反応を防止することが特開昭55−
95681号公報及び同58−190876号公報に開示されてい
る。As a method for suppressing the hydration reaction of the added metal, it is known that a resin and a metal are heated and mixed to perform a coating treatment on the metal to impart hydrophobicity to the metal surface and prevent the hydration reaction.
Nos. 95681 and 58-190876.
しかし、これらの対策は原料調製段階に粉砕工程を必
要とし、粉砕時に金属が表面に露出するため水和反応を
完全に制御することは不可能である。However, these measures require a pulverizing step in the raw material preparation stage, and the metal is exposed to the surface during the pulverization, so that it is impossible to completely control the hydration reaction.
本発明において解決すべき課題は、炭素含有耐火材料
の出発原料としての炭素材料の酸化防止と共に、炭素含
有耐火材料の耐酸化性，耐食性の改善と熱間強度の向上
のために添加される金属の水和反応の発生を防止して、
それらの配合原料の特性を充分に発揮させることにあ
る。The problem to be solved in the present invention is to prevent the carbon material as a starting material of the carbon-containing refractory material from being oxidized, and to improve the oxidation resistance, corrosion resistance, and hot strength of the carbon-containing refractory material. To prevent the occurrence of hydration reaction of
The purpose of the present invention is to sufficiently exhibit the characteristics of these compounding raw materials.
本発明のカーボン含有耐火物用原料は、配合金属と固
定炭素の高い樹脂溶液との混合物を、噴射造粒とするこ
とによって得られるもので、同混合物が硼素含有化合物
およびSiCの１種又は２種以上の化合物を含有せしめる
ことによってカーボン材の酸化をより効果的に防止でき
る。The carbon-containing refractory raw material of the present invention is obtained by subjecting a mixture of a compounded metal and a resin solution having a high fixed carbon to injection granulation, wherein the mixture is one or two or more of a boron-containing compound and SiC. Oxidation of the carbon material can be more effectively prevented by including at least one compound.
本発明は、金属の被覆手段として、噴射造粒法を用い
るものであるので、金属部分が露出することなく樹脂に
より被覆され、しかも被覆樹脂の厚さを任意に変更する
ことが可能となる。Since the present invention uses the injection granulation method as the metal coating means, the metal portion is coated with the resin without being exposed, and the thickness of the coating resin can be arbitrarily changed.
また、粒度調整を行うのに際して粉砕工程を必要とせ
ず、分級のみで粒度調整が可能となる。In addition, a pulverizing step is not required for adjusting the particle size, and the particle size can be adjusted only by classification.
さらに、添加金属の表面が露出することがなくなり、
金属の水和反応の発生を防止できるので、高温域におけ
る耐火物の強度を高めるという配合金属自体の効果を充
分に発揮させることが可能となる。Furthermore, the surface of the added metal is no longer exposed,
Since the occurrence of the hydration reaction of the metal can be prevented, it is possible to sufficiently exert the effect of the compounded metal itself in increasing the strength of the refractory in a high temperature range.
本発明に用いる金属としては、特に制限はないが、ア
ルミニウムあるいはマグネシウムのように水和反応を容
易に生じる金属の場合に特に効果がある。本発明に適用
する金属の粒度も特に制限を受けないが、造粒子を配合
に添加した場合の分散性などを考慮すれば100〜200メッ
シュ程度が好ましい。The metal used in the present invention is not particularly limited, but is particularly effective in the case of a metal which easily undergoes a hydration reaction, such as aluminum or magnesium. The particle size of the metal used in the present invention is not particularly limited, but is preferably about 100 to 200 mesh in consideration of the dispersibility when the granulated particles are added to the compound.
本発明は、カーボン材としてピッチのような非晶質の
カーボンを使用することが多い不定形耐火物に適用する
のに好適である。INDUSTRIAL APPLICABILITY The present invention is suitable for application to irregular-shaped refractories which often use amorphous carbon such as pitch as a carbon material.
ピッチのような非晶質カーボンの酸化開始温度と、金
属例えばアルミニウムの融点を比較すると前者の方が低
い。この様な場合、金属の軟化，溶融，分散が不十分な
ため、金属のみで酸化防止を図ることは困難である。When the oxidation start temperature of amorphous carbon such as pitch is compared with the melting point of a metal such as aluminum, the former is lower. In such a case, since the softening, melting and dispersion of the metal are insufficient, it is difficult to prevent the oxidation only with the metal.
硼砂，硼酸、硼珪酸ガラス等の硼素含有化合物は、カ
ーボンの酸化開始温度以下の温度で軟化溶融し、ガラス
被膜を生成するため、カーボンの酸化防止剤として公知
である。Boron-containing compounds such as borax, boric acid, and borosilicate glass are known as carbon antioxidants because they soften and melt at a temperature lower than the oxidation start temperature of carbon to form a glass film.
しかしながら、この硼素含有化合物自体はキャスタブ
ル耐火物の硬化遅延剤であるため、多量に使用すると施
工体を得ることができなくなるため、キャスタブル耐火
物に酸化防止を目的として、量的に添加することは困難
であった。However, since the boron-containing compound itself is a hardening retarder for castable refractories, if it is used in a large amount, it will not be possible to obtain a construction body. Therefore, it is not possible to quantitatively add castable refractories to castable refractories in order to prevent oxidation. It was difficult.
本発明によれば、硼酸のように水に溶解し作業性を阻
害する素材でも、その溶出を防止することが可能であ
り、酸化防止材としての機能を付与することが可能とな
り、ピッチの様な易酸化性カーボンの耐酸化性を向上さ
せることが可能である。According to the present invention, even a material that dissolves in water and hinders workability, such as boric acid, can be prevented from being eluted, and can have a function as an antioxidant, and can be used as a pitch. It is possible to improve the oxidation resistance of easily oxidizable carbon.
酸化防止材としては硼酸，硼砂，硼珪酸ガラスあるい
はB4C等の様にカーボンの酸化開始温度以下の温度でガ
ラス被膜を生成する化合物が有効であり、これらのほか
に例えばSiCのような酸化防止材を使用することも可能
である。As an antioxidant, compounds which form a glass film at a temperature lower than the oxidation start temperature of carbon, such as boric acid, borax, borosilicate glass or B 4 C, are effective. It is also possible to use a barrier.
本発明に用いる樹脂は、天然，合成により得られるあ
らゆる樹脂が使用可能であるが、酸化防止をより効果的
に行うためにピッチ，フェノール樹脂，フラン樹脂など
固定炭素の高い樹脂が好ましい。固定炭素量を高めるた
めに、樹脂類の他に更に鱗状黒鉛，土状黒鉛，人造黒
鉛，コークス，高軟化点ピッチなどを併用することも可
能である。As the resin used in the present invention, any resin obtained by natural or synthetic methods can be used, but a resin having a high fixed carbon such as a pitch, a phenol resin or a furan resin is preferable for more effectively preventing oxidation. In order to increase the amount of fixed carbon, scaly graphite, earthy graphite, artificial graphite, coke, high softening point pitch, etc. can be used in addition to resins.
実施例1. ピッチ50重量部と金属アルミニウム（純度99％，平均
粒径0.1mm）50重量部とを加熱混合溶解せしめて噴射造
粒法により造粒し、平均粒径0.3mmの造粒子を得た。Example 1. 50 parts by weight of a pitch and 50 parts by weight of metal aluminum (purity: 99%, average particle size: 0.1 mm) were heated, mixed and melted, and granulated by a spray granulation method to form granules having an average particle size of 0.3 mm. Obtained.
この造粒子を粒度調整したアルミナ質流し込み用耐火
材に５重量％添加し、５重量％の水と共に３分間混練
し、金枠に鋳込み、発熱温度を測定することにより、樹
脂被覆した金属アルミの水和安定性について調査した。5% by weight of the granulated particles was added to the adjusted refractory material for alumina casting, kneaded with 5% by weight of water for 3 minutes, cast into a metal frame, and measured the heat generation temperature to obtain a resin-coated metal aluminum. The hydration stability was investigated.
テスト結果を第１表に示す。 Table 1 shows the test results.
比較品１に用いたAl粒度：平均粒径0.1mm 比較品１に用いたピッチ造粒したAlの製造法：ピッチ50
重量部,Al（平均粒径0.1mm,純度99％）50重量部をニー
ダーにて加熱混合の後冷却し粉砕した。粒度は平均粒径
0.3mm,養生は以下全て35℃で行い、見掛け気孔率は110
℃×24時間後に測定したものである。 Al particle size used for comparative product 1: average particle size 0.1 mm Manufacturing method of pitch-granulated Al used for comparative product 1: pitch 50
Parts by weight and 50 parts by weight of Al (average particle size: 0.1 mm, purity: 99%) were mixed by heating in a kneader, then cooled and pulverized. Particle size is average particle size
0.3 mm, curing is performed at 35 ° C, apparent porosity is 110
It was measured after 24 hours at ° C.
同実施例によって、本発明によれば、Alの水和反応が
生じないため、組織劣化も招かずに水を使用する不定形
材料に金属アルミニウムを比較的多量に使用することが
可能であることが判る。According to the present embodiment, according to the present invention, since a hydration reaction of Al does not occur, it is possible to use a relatively large amount of metallic aluminum in an amorphous material using water without causing structural deterioration. I understand.
実施例2. A:ピッチ50重量部，アルミニウム50重量部 B:ピッチ50重量部，アルミニウム40重量部， 硼砂10重量部 C:ピッチ50重量部，アルミニウム30重量部， 硼砂10重量部,B4C10重量部 からなる平均粒径0.3mmの造粒子を噴射造粒法により得
た。Example 2 A: 50 parts by weight of pitch, 50 parts by weight of aluminum B: 50 parts by weight of pitch, 40 parts by weight of aluminum, 10 parts by weight of borax C: 50 parts by weight of pitch, 30 parts by weight of aluminum, 10 parts by weight of borax, B 4 Granulated particles having an average particle diameter of 0.3 mm composed of C10 parts by weight were obtained by a spray granulation method.
この造粒子をAl2O360％,SiC35％，ピッチ５％の樋用
流し込み材に適用し、耐酸化性，耐食性，熱間強度につ
いて調査した。The granulated particles were applied to a casting material for a gutter of 60% Al 2 O 3 , 35% SiC, and 5% pitch, and the oxidation resistance, corrosion resistance, and hot strength were investigated.
その結果を第２表に示す。 Table 2 shows the results.
酸化テストは50mmφ×100mmHのサンプルを1000℃×3H
酸化焼成した後に二つに切断し、表面の白色層の厚さを
測定した。 For the oxidation test, a sample of 50mmφ × 100mmH was used at 1000 ℃ × 3H
After oxidizing and firing, the resultant was cut into two pieces, and the thickness of the white layer on the surface was measured.
溶損指数は回転ドラム法1600℃×0.5H×10回侵食剤
高炉スラグ／銑鉄＝8/2の条件下で、通常品（Ｇ）の溶
損速度を100として指数で示した（数字の小さいほうが
耐食性良好）。The erosion index is 1600 ° C x 0.5H x 10 times erosion agent by rotary drum method
Under the condition of blast furnace slag / pig iron = 8/2, the erosion rate of the normal product (G) was set to 100 and indicated as an index (the smaller the number, the better the corrosion resistance).
熱間強度は、サンプルサイズ40×40×160mmで、1450
℃×1H（N2気流中）の測定条件で行った。The hot strength is 1450 for sample size 40 × 40 × 160mm.
C. × 1H (in a stream of N 2 ).
これによって、本発明によれば、硼砂のように水に溶
解し、不定形材の作業性を大幅に阻害するため、多量に
使用することが不可能であった素材も使用するとが可能
となり、材料の機能を大幅に改良することが可能である
ことが判る。Thereby, according to the present invention, it is possible to use a material which cannot be used in large quantities because it is dissolved in water like borax and greatly impairs the workability of the irregularly shaped material. It can be seen that the function of the material can be greatly improved.
本発明による造粒子をAl2O360％,SiC35％の樋用流し
込み材に適用し、製鉄所大樋スラグゾーンにおいて実用
試験を行った結果を第４表に示す（試用期間１ヶ月）。The granulated particles according to the present invention Al 2 O 3 60%, applied to the casting material for SiC35% of the trough, the results of the practical test in steelworks Ohi slag zone shown in Table 4 (trial 1 month).
本発明による造粒子を適用した材料は、従来材に比較
して25％耐用が向上した。The material to which the granulated particles according to the present invention is applied has a 25% higher durability than the conventional material.
常に酸化雰囲気にさらされる肩部における損耗が非常
に軽微であり、本発明の優位性が確認された。The wear on the shoulder constantly exposed to the oxidizing atmosphere was very slight, confirming the superiority of the present invention.
本発明の説明をアルミナ−SiC−カーボン質材料で行
ったが、材料としては、マグネシア−カーボン質，マグ
ネシア−SiC−カーボン質，ジルコニア−SiC−カーボン
質，アルミナ−窒化けい素−カーボン質のように、カー
ボン,SiC等の非酸化物を含む種々の定形，不定形材料に
対して応用できる。 Although the description of the present invention has been made with alumina-SiC-carbonaceous materials, examples of materials include magnesia-carbonaceous, magnesia-SiC-carbonaceous, zirconia-SiC-carbonaceous, and alumina-silicon nitride-carbonaceous. In addition, it can be applied to various regular and irregular materials including non-oxides such as carbon and SiC.
本発明によれば、Alの水和反応が生じないため、組織
劣化も招かずに水を使用する不定形材料にAlを量的に使
用することが可能である。ADVANTAGE OF THE INVENTION According to this invention, since the hydration reaction of Al does not generate | occur | produce, it is possible to quantitatively use Al for the amorphous material which uses water, without causing a structural deterioration.
これによって、本発明によれば、硼砂のように水に溶
解し、不定形材の作業性を大幅に阻害するため、多量に
使用することが不可能であった素材も使用することが可
能となり、材料の機能を大幅に改良することが可能であ
ることが判る。Thereby, according to the present invention, it is possible to use a material which cannot be used in large quantities because it is dissolved in water such as borax and greatly impairs the workability of the irregularly shaped material. It can be seen that the function of the material can be greatly improved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/00 Ｗ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Reference number in the agency FI Technical display location C04B 35/00 W
Claims (2)
を溶融し、噴射造粒することを特徴とするカーボン含有
耐火物用原料の調製方法。1. A method for preparing a carbon-containing refractory raw material, comprising melting a mixture of a compounded metal and a resin having a high fixed carbon, followed by injection granulation.
又は２種以上の化合物を含有せしめてなることを特徴と
する特許請求の範囲第１項に記載のカーボン含有耐火物
用原料の調製方法。2. The method for preparing a carbon-containing refractory raw material according to claim 1, wherein the mixture contains a boron-containing compound and one or more compounds of SiC. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174302A JP2702510B2 (en) | 1988-07-12 | 1988-07-12 | Preparation method of raw materials for carbon-containing refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174302A JP2702510B2 (en) | 1988-07-12 | 1988-07-12 | Preparation method of raw materials for carbon-containing refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0226816A JPH0226816A (en) | 1990-01-29 |
| JP2702510B2 true JP2702510B2 (en) | 1998-01-21 |
Family
ID=15976289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63174302A Expired - Fee Related JP2702510B2 (en) | 1988-07-12 | 1988-07-12 | Preparation method of raw materials for carbon-containing refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2702510B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100471356B1 (en) * | 2001-07-06 | 2005-03-08 | 조선내화 주식회사 | carbon for refractories & refractories with carbon |
| CN106424664A (en) * | 2015-08-06 | 2017-02-22 | 李康 | Production process of silicon carbide (emery) composite wear resisting material |
| CN109970458B (en) * | 2017-12-28 | 2022-03-01 | 埃肯硅材料(兰州)有限公司 | Modified carbonaceous chute and preparation method thereof |
-
1988
- 1988-07-12 JP JP63174302A patent/JP2702510B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0226816A (en) | 1990-01-29 |
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