JP3785200B2 - Carbon-containing basic refractories - Google Patents
Carbon-containing basic refractories Download PDFInfo
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- JP3785200B2 JP3785200B2 JP04260295A JP4260295A JP3785200B2 JP 3785200 B2 JP3785200 B2 JP 3785200B2 JP 04260295 A JP04260295 A JP 04260295A JP 4260295 A JP4260295 A JP 4260295A JP 3785200 B2 JP3785200 B2 JP 3785200B2
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Description
【０００１】
【産業上の利用分野】
本発明は、転炉等の溶融金属精錬炉の内張りに用いられる炭素含有塩基性耐火物に関するものである。
【０００２】
【従来の技術】
溶融金属精錬炉の内張りに用いられる耐火物としては、耐スラグ性、耐熱衝撃性に優れたＭｇＯ−炭素系の塩基性耐火物が多用され、かなりの高成績をあげている。さらに、耐スラグ性を向上させるためには電融マグネシアクリンカーを原料として用いられることが効果的とされている。ＭｇＯ−炭素系の塩基性耐火物の損耗は、スラグがマグネシアの結晶粒界に浸透し、粒界生成物と反応して低融点物質を形成し、マグネシア結晶粒界を分断することにより促進される。
【０００３】
そこで、焼結マグネシアクリンカーに比べて結晶粒界および粒界生成物の少ない電融マグネシアクリンカーを適用することにより、粒界へのスラグ浸透の割合が少なくなり、高耐食性が得られることになる。一般に電融マグネシアクリンカーは、海水を原料とした酸化マグネシウムを電融することにより得られるが、電融する工程に加えて海水から酸化マグネシウムを得る工程が加わるため価格が非常に高くなる。そこで、安価で高耐食性を有するＭｇＯ−炭素系の塩基性耐火物を得るために、天然マグネサイトを原料とする安価な電融マグネシアクリンカーを使用したものも提案されている（特開平６−１０７４５３号公報参照）。
【０００４】
【発明が解決しようとする課題】
本発明では、不純物成分を比較的多く含む安価なマグネシアクリンカーを有効活用することにより、安価で高耐食性を有するＭｇＯ−炭素系の塩基性耐火物を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明による炭素含有塩基性耐火物は、ＭｇＯ含有量が９４重量％以上９７．５８重量％以下であり、残りの不純物成分のうちＣａＯとＳｉＯ2の合計が３重量％未満であって、かつ、２３００℃以上の高温で製造してＡｌ2Ｏ3およびＦｅ2Ｏ3成分をペリクレース粒内に固溶させたマグネシアクリンカー６０部以上９４部以下と、炭素源６部以上４０部以下とからなる耐火物原料１００部に、さらに外掛けでバインダー、および酸化防止剤を添加して得られる
【０００６】
また、本発明における炭素含有塩基性耐火物の製造方法は、ＭｇＯ含有量が９４重量％以上９７．５８重量％以下であり、残りの不純物成分のうちＣａＯとＳｉＯ2の合計が３重量％未満であるマグネシア原料を２３００℃以上の高温で処理を施して、Ａｌ2Ｏ3及びＦｅ2Ｏ3成分をペリクレース粒内に固溶させたマグネシアクリンカーを製造し、該マグネシアクリンカー６０部以上９４部以下と、炭素源６部以上４０部以下に、さらに外掛けでバインダー、及び酸化防止剤を添加配合して混練した後、成形、乾燥することを特徴とする。
【０００７】
【作用】
以下、本発明について作用とともに詳細に説明する。
本発明者らは、マグネシアクリンカーを詳細に解析して以下の事項を見出した。マグネシアクリンカーには、主成分であるＭｇＯの他に不純物成分としてＣａＯ、ＳｉＯ2 、Ａｌ2 Ｏ3 、Ｆｅ2 Ｏ3 等が含まれる。アーク炉、あるいは、タングステンヒーター等を熱源とする超高温加熱炉で、約２３００℃以上の高温過程を経て製造したマグネシアクリンカーでは、これらの成分のうちＣａＯ、およびＳｉＯ2 はＭｇＯの結晶粒界に存在して粒界生成物を形成する。また、Ａｌ2 Ｏ3 、Ｆｅ2 Ｏ3 、および一部のＣａＯはＭｇＯ粒内に粒内析出物として固定される。
【０００８】
前述したように、ＭｇＯ−炭素系の塩基性耐火物の損耗は、スラグとマグネシアクリンカー中の粒界生成物とが反応してＭｇＯ結晶粒界を分断することにより促進される。マグネシアクリンカー中の不純物成分の総量が多くても粒界生成物を形成するＣａＯ、およびＳｉＯ2 の合計量が少ない粒界生成物の量が少なくなり、このマグネシアクリンカーを使用したＭｇＯ−炭素系の塩基性耐火物の損耗は抑制される。
【０００９】
そこで、本発明で使用するマグネシアクリンカーを以下のように定めた。すなわち、マグネシアクリンカー中に含まれるＣａＯ、およびＳｉＯ2 の合計量を３重量％未満とし、かつ、約２３００℃以上の高温で熱処理を施してＡｌ2 Ｏ3 およびＦｅ2 Ｏ3 成分をペリクレース粒内に固溶させたものとした。不純物成分がこの範囲であると、マグネシアクリンカー中に形成される粒界生成物の量が少なくなり、このマグネシアクリンカーを使用したＭｇＯ−炭素系の塩基性耐火物の耐食性は優れているからである。
【００１０】
もし、マグネシアクリンカー中に含まれるＣａＯ、およびＳｉＯ2 の合計量が３重量％以上になると、マグネシアクリンカー中の結晶粒界および粒界生成物の生成量が多くなり、これを使用したＭｇＯ−炭素系の塩基性耐火物の耐食性は劣り好ましくない。また、約２３００℃以上の高温処理を施さないマグネシアクリンカーでは、含まれている不純物のほとんどが粒界生成物を形成するため粒界生成物の量が多くなり、このマグネシアクリンカーを使用したＭｇＯ−炭素系の塩基性耐火物のスラグによる損耗は大きくなる。
【００１１】
ところで、マグネシアクリンカー中に含まれるＣａＯとＳｉＯ2 のモル比により形成される粒界生成物の鉱物層が異なる。ＣａＯ／ＳｉＯ2 の値が小さく、特に約１〜２の範囲では生成する鉱物層の融点が低くなって耐食性が悪くなる傾向があるため、ＣａＯ／ＳｉＯ2 の値が２以上のマグネシアクリンカーがよく用いられてきた。しかし、本発明では、電融マグネシアクリンカー中に含まれるＣａＯ、およびＳｉＯ2 の合計量を３重量％未満とし、かつ、Ａｌ2 Ｏ3 およびＦｅ2 Ｏ3 成分をペリクレース粒内に固溶させたマグネシアクリンカーを用いることによって、粒界生成物の生成量が少なくなるため、融点が低い粒界生成物が形成されても高い耐食性を有する。
【００１２】
ＭｇＯ含有量を９４重量％以上９７．５８重量％以下としたのは、この範囲であるとマグネシアクリンカー中のＭｇＯ粒内に形成される粒内析出物の量はさほど多くなく、これを使用したＭｇＯ−炭素系の塩基性耐火物の高温強度が優れているからである。従って、ＭｇＯ含有量が９４重量％未満であると、マグネシアクリンカー中のＭｇＯ粒内に形成される粒内析出物が多くなり、これを使用したＭｇＯ−炭素系の塩基性耐火物の高温強度が劣る。
【００１３】
本発明の炭素含有塩基性耐火物において、用いるマグネシアクリンカー含有量を６０部以上９４部以下としたのは、この範囲で耐食性、耐熱衝撃性に優れるからである。すなわち、マグネシアクリンカー含有量が６０部未満になると、耐酸化性が著しく低下し、９４部を超えると耐熱衝撃性、耐食性、特に耐スラグ浸潤性が著しく低下する。
【００１４】
炭素源としては、天然または人造黒鉛、メンフェーズカーボン、コークス、カーボンブラック等を用い、できるだけ高純度のものが望ましい。バインダーとしては、フェノール樹脂、フラン樹脂、ピッチ等を用い、添加量はマグネシアクリンカーと炭素源との合計を１００部として外掛けで２〜５部程度が望ましい。酸化防止剤としては、金属Ａｌ、金属Ｓｉ、Ａｌ−ＭｇＯ合金等を用い、添加量はマグネシアクリンカーと炭素源との合計を１００部として外掛けで５部以下が望ましい。
【００１５】
【実施例】
以下、実施例に基づき本発明を説明する。但し、本発明はこれらの実施例に限定されるものではない。
【００１６】
表１に示すような組成の２３００℃以上の温度で製造したマグネシア（ＭｇＯ）クリンカーを用い、表中に示す原料配合組成で混練、真空フリクション形成、乾燥（９０℃×２４ｈｒｓ．）、硬化処理（２５０℃×１０ｈｒｓ．）を実施してＭｇＯ−炭素系の塩基性耐火物を得た。
【００１７】
表１に示してあるように、本発明の実施例１〜８のＭｇＯ−炭素系の塩基性耐火物は溶損指数が１１５以下で耐食性に優れている。
【００１８】
また、表２の比較例１〜４には、本発明の範囲から外れた組成の天然マグネサイトを原料とする電融マグネシアクリンカーを使用した場合のＭｇＯ−炭素系の塩基性耐火物の特性を示す。表１の本発明の実施例に比較して耐食性、あるいはそれに加えて高温強度が劣る。
【００１９】
比較例５および６は、本発明と同じ組成であるが、１８００℃の熱処理を経て製造されたマグネシアクリンカーを使用した場合のＭｇＯ−炭素系の塩基性耐火物の特性を示す。ここでも表１の実施例に比較して耐食性が劣る。
【００２０】
さらに、表２の比較例７および８には、マグネシアクリンカーと炭素の配合割合が本発明の範囲から外れたＭｇＯ−炭素系の塩基性耐火物の特性を示す。実施例に比較して高温強度、耐食性、耐酸化性、あるいは耐熱衝撃性で劣る。なお、表２において、比較例５および６以外の熱処理温度は、２３００℃以上である。
【００２１】
【表１Ａ】
【表１Ｂ】
【表２Ａ】
【表２Ｂ】
【発明の効果】
本発明によって、従来の海水を原料とした酸化マグネシウムを電融して得られる不純物成分の総量が少ないマグネシアクリンカーを使用した場合のＭｇＯ−炭素系の塩基性耐火物と耐食性、耐熱衝撃性、耐酸化性が同等で、従来品に比べて安価なＭｇＯ−炭素系の塩基性耐火物が得られる。このことにより炉材コストの削減が可能となる。[0001]
[Industrial application fields]
The present invention relates to a carbon-containing basic refractory used for the lining of a molten metal refining furnace such as a converter.
[0002]
[Prior art]
As a refractory used for the lining of a molten metal refining furnace, an MgO-carbon basic refractory excellent in slag resistance and thermal shock resistance is frequently used, and has achieved considerably high results. Furthermore, in order to improve the slag resistance, it is considered effective to use an electrofused magnesia clinker as a raw material. The wear of MgO-carbon based refractories is accelerated by slag penetrating into the magnesia grain boundaries, reacting with the grain boundary products to form a low melting point material and breaking up the magnesia grain boundaries. The
[0003]
Therefore, by applying an electrofused magnesia clinker with fewer crystal grain boundaries and grain boundary products than the sintered magnesia clinker, the ratio of slag penetration into the grain boundary is reduced, and high corrosion resistance can be obtained. Generally, an electrofused magnesia clinker is obtained by electromelting magnesium oxide using seawater as a raw material. However, since the process of obtaining magnesium oxide from seawater is added to the process of electromelting, the price becomes very high. Therefore, in order to obtain an inexpensive MgO-carbon basic refractory having high corrosion resistance, a material using an inexpensive electrofused magnesia clinker made of natural magnesite has been proposed (Japanese Patent Laid-Open No. 6-107453). No. publication).
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an inexpensive MgO-carbon basic refractory having high corrosion resistance by effectively utilizing an inexpensive magnesia clinker containing a relatively large amount of impurity components.
[0005]
[Means for Solving the Problems]
The carbon-containing basic refractory according to the present invention has a MgO content of 94 wt% or more and 97.58 wt% or less , and the total of CaO and SiO 2 among the remaining impurity components is less than 3 wt%, and It consists of 60 parts to 94 parts of magnesia clinker prepared at a high temperature of 2300 ° C. or higher and having Al 2 O 3 and Fe 2 O 3 components dissolved in the periclase grains, and 6 parts to 40 parts of carbon source. It is obtained by adding a binder and an antioxidant as an outer shell to 100 parts of a refractory raw material.
Further, in the method for producing a carbon-containing basic refractory according to the present invention, the MgO content is 94 wt% or more and 97.58 wt% or less , and among the remaining impurity components, the total of CaO and SiO 2 is less than 3 wt%. A magnesia clinker in which Al 2 O 3 and Fe 2 O 3 components are solid-dissolved in periclase grains is processed by treating the magnesia raw material at a high temperature of 2300 ° C. or more, and the magnesia clinker is 60 parts or more and 94 parts or less. In addition, a binder and an antioxidant are further added and blended with 6 parts or more and 40 parts or less of a carbon source, and then molded and dried.
[0007]
[Action]
Hereinafter, the present invention will be described in detail together with the operation.
The present inventors have analyzed magnesia clinker in detail and found the following matters. The magnesia clinker includes CaO, SiO 2 , Al 2 O 3 , Fe 2 O 3 and the like as impurity components in addition to MgO as a main component. In the magnesia clinker manufactured through a high temperature process of about 2300 ° C or higher in an arc furnace or an ultra-high temperature heating furnace using a tungsten heater as a heat source, among these components, CaO and SiO 2 are present at the grain boundaries of MgO. Present to form grain boundary products. Al 2 O 3 , Fe 2 O 3 , and a part of CaO are fixed as intragranular precipitates in the MgO grains.
[0008]
As described above, the wear of the MgO-carbon basic refractory is promoted by the slag and the grain boundary product in the magnesia clinker reacting to break the MgO crystal grain boundary. Even if the total amount of impurity components in the magnesia clinker is large, the amount of CaO forming the grain boundary product and the grain boundary product having a small total amount of SiO 2 is reduced, and the MgO-carbon system using this magnesia clinker is reduced. Wear of the basic refractory is suppressed.
[0009]
Therefore, the magnesia clinker used in the present invention was determined as follows. That is, the total amount of CaO and SiO 2 contained in the magnesia clinker is set to less than 3% by weight, and heat treatment is performed at a high temperature of about 2300 ° C. or higher so that the Al 2 O 3 and Fe 2 O 3 components are contained in the periclase grains. It was assumed to be a solid solution. If the impurity component is within this range, the amount of grain boundary products formed in the magnesia clinker is reduced, and the corrosion resistance of the MgO-carbon basic refractory using this magnesia clinker is excellent. .
[0010]
If the total amount of CaO and SiO 2 contained in the magnesia clinker is 3% by weight or more, the production amount of crystal grain boundaries and grain boundary products in the magnesia clinker increases, and MgO-carbon using this increases. The corrosion resistance of the basic refractories is not preferable. In addition, in the magnesia clinker that is not subjected to a high temperature treatment of about 2300 ° C. or higher, most of the impurities contained therein form a grain boundary product, so that the amount of the grain boundary product increases, and the MgO − using this magnesia clinker Wear due to slag of carbon-based basic refractories increases.
[0011]
By the way, the mineral layer of the grain boundary product formed by the molar ratio of CaO and SiO 2 contained in the magnesia clinker is different. Since the value of CaO / SiO 2 is small, especially in the range of about 1-2, the melting point of the resulting mineral layer tends to be low and the corrosion resistance tends to be poor. Therefore, magnesia clinker with a CaO / SiO 2 value of 2 or more is good. Has been used. However, in the present invention, the total amount of CaO and SiO 2 contained in the electrofused magnesia clinker is less than 3% by weight, and the Al 2 O 3 and Fe 2 O 3 components are dissolved in the periclase grains. By using a magnesia clinker, the amount of grain boundary products is reduced, so that even if a grain boundary product having a low melting point is formed, it has high corrosion resistance.
[0012]
If the MgO content is 94 wt% or more and 97.58 wt% or less , the amount of intragranular precipitates formed in the MgO grains in the magnesia clinker is not so large, and this was used. This is because the high-temperature strength of the MgO-carbon basic refractory is excellent. Accordingly, when the MgO content is less than 94% by weight, the intragranular precipitates formed in the MgO grains in the magnesia clinker increase, and the high temperature strength of the MgO-carbon basic refractory using this is high. Inferior.
[0013]
The reason why the magnesia clinker content used in the carbon-containing basic refractory of the present invention is 60 parts or more and 94 parts or less is that in this range, the corrosion resistance and the thermal shock resistance are excellent. That is, when the magnesia clinker content is less than 60 parts, the oxidation resistance is remarkably reduced, and when it exceeds 94 parts, the thermal shock resistance and corrosion resistance, particularly the slag infiltration resistance are remarkably lowered.
[0014]
As the carbon source, natural or artificial graphite, menphase carbon, coke, carbon black, etc. are used, and those having the highest possible purity are desirable. As the binder, phenol resin, furan resin, pitch, or the like is used, and the addition amount is preferably about 2 to 5 parts as an outer coating with the total of magnesia clinker and carbon source being 100 parts. As the antioxidant, metal Al, metal Si, Al—MgO alloy or the like is used, and the addition amount is desirably 5 parts or less as an outer coating with the total of the magnesia clinker and the carbon source being 100 parts.
[0015]
【Example】
Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to these examples.
[0016]
Using a magnesia (MgO) clinker having a composition as shown in Table 1 manufactured at a temperature of 2300 ° C. or higher, kneading, vacuum friction formation, drying (90 ° C. × 24 hrs.), Curing treatment with the raw material composition shown in the table ( 250 ° C. × 10 hrs.) Was performed to obtain an MgO-carbon basic refractory.
[0017]
As shown in Table 1, the MgO-carbon basic refractories of Examples 1 to 8 of the present invention have a corrosion index of 115 or less and excellent corrosion resistance.
[0018]
Further, Comparative Examples 1 to 4 in Table 2 show the characteristics of MgO-carbon basic refractories when using an electrofused magnesia clinker made of natural magnesite having a composition outside the scope of the present invention. Show. Compared with the Example of this invention of Table 1, it is inferior in corrosion resistance, or in addition, high temperature strength.
[0019]
Comparative Examples 5 and 6 have the same composition as the present invention, but show the properties of MgO-carbon based basic refractories when using magnesia clinker manufactured through heat treatment at 1800 ° C. Again, the corrosion resistance is inferior to the examples in Table 1.
[0020]
Further, Comparative Examples 7 and 8 in Table 2 show the characteristics of MgO-carbon based refractories in which the blending ratio of magnesia clinker and carbon is out of the scope of the present invention. It is inferior in high temperature strength, corrosion resistance, oxidation resistance, or thermal shock resistance as compared with the examples. In Table 2, the heat treatment temperature other than Comparative Examples 5 and 6 is 2300 ° C. or higher.
[0021]
[Table 1A]
[Table 1B]
[Table 2A]
[Table 2B]
【The invention's effect】
According to the present invention, MgO-carbon basic refractory and corrosion resistance, thermal shock resistance, acid resistance when using a magnesia clinker with a small total amount of impurity components obtained by electromelting magnesium oxide from seawater as a raw material. It is possible to obtain a basic refractory based on MgO-carbon that has the same chemical conversion properties and is cheaper than conventional products. This makes it possible to reduce the furnace material cost.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04260295A JP3785200B2 (en) | 1995-02-08 | 1995-02-08 | Carbon-containing basic refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04260295A JP3785200B2 (en) | 1995-02-08 | 1995-02-08 | Carbon-containing basic refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08217529A JPH08217529A (en) | 1996-08-27 |
| JP3785200B2 true JP3785200B2 (en) | 2006-06-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04260295A Expired - Lifetime JP3785200B2 (en) | 1995-02-08 | 1995-02-08 | Carbon-containing basic refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3785200B2 (en) |
-
1995
- 1995-02-08 JP JP04260295A patent/JP3785200B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08217529A (en) | 1996-08-27 |
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