JP2002145673A - Refractory for converter tapping hole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such refractories for a converter tapping hole consisting of a sleeve fitted to a tapping section of a converter and a block(s) laid on the periphery of the sleeve, that not only the oxidation resistance, spalling resistance, dissolution resistance and wear resistance of each of the refractories are sufficient to meet the respective requirements and the service durability of such a refractory for the tapping hole sleeve can be improved but also accordingly, the frequencies of repair and replacement of the tapping hole sleeve can be reduced and further, an improvement in operation rate of the converter can be realized. SOLUTION: Each of a part or all of the refractories for a converter tapping hole consisting of a sleeve fitted to a tapping section of a converter and a block(s) laid on the periphery of the sleeve, consists of a spinel-containing formed body the production process of which comprises: adding 0.1-20 mass % (on the outer percentage basis) of a binder to 100 mass % of a spinel raw material consisting essentially of magnesia and alumina; kneading the resulting mixture; forming the kneaded material into a green body; and drying the green body, and optionally, thereafter further firing the dried body in a non-oxidizing atmosphere, to produce the objective formed body; wherein the spinel-containing formed body has a <=15 mass % unavoidable impurity content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a converter which is suitable for use in a converter tapping hole comprising a sleeve disposed at a converter tapping section and a block disposed around the sleeve. The present invention relates to a spinel type refractory for a tap hole of a furnace.

[0002]

2. Description of the Related Art A magnesia-carbon refractory excellent in corrosion resistance and spalling resistance is used for a sleeve and a block refractory of a converter tap hole used under a condition of large thermal shock. Since the magnesia-carbon refractory was developed, the service life of the converter outlet steel refractory has been greatly improved. However, magnesia-carbon refractories also have various drawbacks, and have been improved.

[0003] For example, a refractory sleeve for a converter tap hole is:
Since the molten steel flows through the inner hole, the entire length direction becomes the working surface, the expansion and shrinkage accompanying heating-cooling is remarkable, and even with magnesia-carbon refractories, cracks due to tensile stress are on the back side. When the cracks develop and reach the operating surface, they may fall off or fall off, or the molten steel or slag may enter the cracks, and the refractory may not be easily dismantled due to the melting damage. In order to solve this problem, Japanese Patent Application Laid-Open No. 6-184617 discloses a sleeve refractory sleeve for converter tapping, wherein the whole is made of magnesia-carbon refractory and contains alumina in the inner periphery. Is disclosed. The invention of the publication discloses that magnesia and alumina react with each other due to heat during use by containing alumina in the inner peripheral portion of the sleeve refractory, and MgO.
An Al ₂ O ₃ -based spinel is formed, and the volume expansion accompanying the reaction densifies the inner peripheral portion of the sleeve refractory to prevent intrusion of molten steel and slag. It is also disclosed that the carbon content of the outer peripheral portion is made smaller than that of the inner peripheral portion.

[0004] A refractory sleeve for a converter tapping outlet is usually used without preheating. Therefore, the molten steel temperature is 1600
There is a temperature difference of ~ 1750 ° C, and when tapping from the converter, the initial impact is generated on the working surface of the tapping sleeve by the thermal shock when it is used without preheating. . Therefore, Japanese Patent Laid-Open No. 9-31520
In the gazette, a sleeve is constituted by a split type of a two-stage to a ten-stage stack, and a converter tapping outlet sleeve characterized in that an inner peripheral surface thereof is coated with an amorphous refractory having a residual expandability. It has been disclosed. It is also disclosed that a sillimanite group mineral such as sillimanite, andalusite or kyanite is used as an amorphous refractory.

[0005] As described above, magnesia-carbon refractory is a material excellent in corrosion resistance and spalling resistance, but has a problem of causing oxidation damage due to oxidation of carbon in the refractory. Therefore, Japanese Patent Application Laid-Open No. 8-259
No. 312, magnesia raw material: 92 to 99% by weight
And a carbon raw material: 1 to 8% by weight, and a metal additive: 0 to 1.5% by weight and a boride: 0 to 0.8% by weight. A low carbon MgO-C refractory for a sleeve is disclosed.

Although not a refractory for a converter tapping outlet, Japanese Patent Publication No. 61-38156 discloses a refractory for a molten metal treatment furnace and a vessel lining, the particle size of which is adjusted for magnesia, calcia, and dolomite. In a carbon-containing basic refractory obtained by adding 5 to 40 parts by weight of a carbon material such as phosphorous graphite, anthracite and carbon black to 60 to 95 parts by weight of a basic material such as spinel, a single fiber is converged inside. A carbon or graphite fiber bundle having a secondary fiber diameter of 0.1 to 3 mm or a mesh made of the fiber bundle, the length direction or the mesh plane of the fiber bundle is directed from the inside of the furnace to the cold end side of the refractory. A refractory is disclosed in which 5 to 100 fiber bundles are disposed per 100 cm ² of cross-sectional area of the refractory so as to be substantially parallel to the axis. The publication discloses the use of carbon or graphite fiber bundles for the purpose of improving the strength characteristics of a carbon-containing basic refractory, and as a method of preventing a phenomenon of peeling through a crack generated by a mechanical impact or the like. It is characterized by having.

Further, Japanese Patent Application Laid-Open No. 63-123857 discloses that a refractory material having a carbon content of 3 to 70 wt% and a balance of refractory aggregate contains 1 to 20 watts of Al powder and / or Al alloy powder.
There is disclosed a method for producing a carbon-containing refractory, which comprises heating a composition added with t% at 300 to 800 ° C. and press-forming. The publication also discloses, as a refractory aggregate occupying the remainder, for example, magnesia clinker, dolomite clinker, spinel clinker, lime clinker,
There is also a description that a material containing alumina, zircon, zirconia, or the like as a main material and a combination of silicon carbide, silicon nitride, silica, fused quartz, chromium oxide, clay, or the like can be used as necessary. The publication states that an increase in porosity during the use stage of the carbon-containing refractory is suppressed, and therefore, the refractory is excellent in corrosion resistance, oxidation resistance and strength after heating.

[0008]

Although various publications are disclosed as described above, no significant improvement in the service life of the tapping sleeve has been obtained. In particular, the service life of the converter main body has reached several thousand charges, whereas the service life of the tapping sleeve is about 1/20 to 1/30. This is due to the special circumstances in the use of refractories for tap holes. In the converter, carbon in the hot metal is burned with oxygen to decarburize, and the decarbonized molten steel flows out of the tapping outlet. At the completion of decarburization, surplus oxygen is dissolved in the molten steel, so the tapping refractory is exposed to the molten steel flow with high oxygen in the steel. It will be used under different harsh conditions. That is, even in a converter, a taphole refractory has a different technical problem from refractories in other parts, and a drastic solution is required.

In general, the properties required for a refractory for a taphole sleeve are oxidation resistance, spalling resistance, erosion resistance and abrasion resistance. The oxidation of magnesia-carbon refractory is caused by the carbon material as described above, and the spalling is caused by a sharp temperature rise at the start of tapping and a sharp drop at the end of tapping. It is believed that erosion is due to slag and wear is due to the strength properties of the material. Of course, it is easy to imagine that these main causes are compounded to promote the damage of the sleeve. The invention described in the above-mentioned publication is intended to solve these main causes, but the fact that the tapping sleeve has not been used to a great extent has not been obtained by using magnesia-carbon refractories. As long as there is no drastic solution.

In view of the above situation, the present inventors reexamined the main causes of low durability of refractories for tapping sleeves.
As a result, a damage mechanism of a tapping sleeve different from the conventional one has been found. That is, it was found that, besides disappearing by oxidation, carbon was also disappeared by rapidly dissolving in molten steel. Further, it was found that relatively large amount of FeO and MnO penetrated into magnesia as the other aggregate.

Here, metals such as aluminum and silicon, alloys such as aluminum-magnesium,
Antioxidants such as boron carbide and calcium boride are effective for preventing carbon oxidation, but are not useful for suppressing the dissolution of carbon in molten steel. On the other hand, penetration of other components into magnesia degrades the properties of magnesia. Further, the expansion coefficient of magnesia itself was relatively large among the refractory materials, and it was also found that spalling resistance was reduced in this respect.

Reviewing the prior art from the above findings, the fact that carbon is used without being protected from molten steel and the use of a large amount of magnesia is effective for greatly improving the durability of the tapping outlet sleeve. It turns out that it is not.

In the above Japanese Patent Application Laid-Open No. 6-184617,
Alumina has been added to magnesia-carbonaceous refractories to produce spinels. However, not all of the added alumina becomes spinel, but a large amount of magnesia and alumina remain. Therefore, erosion greatly advances due to the influence of alumina. Further, since spinel is accompanied by a large volume expansion when it is formed, cracks are formed and spalling resistance is reduced. Furthermore, since the reaction between magnesia and carbon occurs before spinel formation,
A dense layer of spinel described later was not generated, and no suppression of dissolution of carbon in molten steel was obtained. The generated spinel becomes a magnesia-coexisting spinel, and a spinel having a theoretical composition cannot be obtained. That is, an effect different from that containing spinel is shown from the beginning. Accordingly, the drawbacks of the magnesia-carbon refractory have not yet been drastically improved, and alumina is easily melted and damaged by the converter slag, so that a significant improvement in service life cannot be obtained.

The coating of amorphous refractories disclosed in Japanese Patent Application Laid-Open No. 9-31520 is effective in suppressing the initial spalling, but the coating is immediately melted away, and the effect disappears in subsequent use. . That is, a significant improvement in service life of the tapping sleeve cannot be obtained.

Furthermore, in Japanese Patent Application Laid-Open No. Hei 8-259,212, since the amount of carbon in the magnesia-carbon refractory is reduced, the dissolution and oxidation of carbon are slight, but a relatively large amount of magnesia is present. Therefore, a significant improvement in service life of the tapping sleeve cannot be obtained.

Japanese Patent Publication No. 61-38156 discloses that
A special form of fiber is blended into the refractory for molten metal processing furnaces and container linings, which provides refractories with excellent resistance to mechanical stress such as impacts, and is used for converter steel outlets. Does not disclose or suggest the use of a refractory containing spinel.

Further, Japanese Patent Application Laid-Open No. 63-123857 discloses that an increase in the porosity of a refractory is suppressed by blending Al powder or the like with a carbon-containing refractory and press-forming while heating.
It only discloses that a refractory having excellent corrosion resistance and oxidation resistance can be provided, but does not disclose or suggest the use of a refractory containing spinel as a refractory for a converter tapping outlet.

Accordingly, it is an object of the present invention not only to improve the durability of a refractory for a tapping mouth sleeve by satisfying oxidation resistance, spalling resistance, erosion resistance and abrasion resistance, but also to its attendant effects. A sleeve disposed in a converter tapping section that can reduce the repair of the tap hole sleeve and reduce the frequency of replacement of the tap hole sleeve, thereby improving the converter operation rate, and a block disposed around the sleeve. It is another object of the present invention to provide a refractory for a converter tapping outlet comprising the refractory.

[0019]

That is, the present invention provides a refractory for a converter tapping outlet comprising a sleeve disposed in a converter tapping section and a block disposed around the sleeve. Part or all of the binder is added in an amount of 0.1 to 100% by mass of a spinel raw material whose main components are magnesia and alumina.
A molded product obtained by adding, kneading, molding and drying in the range of 1 to 20% by mass and then calcining or not calcining in a non-oxidizing atmosphere, and the amount of unavoidable impurities of the molded body is 15% by mass. % Or less of a refractory for a converter tapping outlet, which is constituted by a spinel-containing refractory molded product having a
"First invention").

Further, according to the present invention, a part or the whole of a refractory for a converter tapping port comprising a sleeve disposed in the converter tapping section and a block disposed around the sleeve is provided. Spinel raw material whose main component is magnesia and alumina is 5
A binder is externally added to a mixture of 0% by mass or more and less than 100% by mass and 50% by mass or less (not including zero) of a carbon material in a range of 0.1 to 20% by mass, kneading, molding, and drying. Thereafter, it is a molded body obtained by firing or not firing in a non-oxidizing atmosphere, and is constituted by a spinel-containing refractory molded body having an unavoidable impurity amount of 15% by mass or less. The present invention relates to a refractory for a converter tap hole (hereinafter, referred to as a "second invention").

Further, according to the present invention, a part or the whole of a refractory for a converter tapping port constituted by a sleeve disposed in the converter tapping section and a block disposed around the sleeve is provided. Spinel raw material whose main component is magnesia and alumina is 5
0 to less than 100% by mass and magnesia raw material 50
Mass% or less (not including zero), a binder is externally added in a range of 0.1 to 20 mass%, kneading,
A molded article obtained by molding or drying and then firing or not firing in a non-oxidizing atmosphere, and comprising a spinel-containing refractory molded article having an inevitable impurity amount of 15% by mass or less in the molded article. The present invention relates to a refractory for a converter tapping outlet (hereinafter referred to as "third invention").

Further, according to the present invention, a part or the whole of a refractory for a converter tapping port constituted by a sleeve disposed in the converter tapping section and a block disposed around the sleeve is provided. Spinel raw material whose main component is magnesia and alumina is 5
0 mass% or more and less than 100 mass%, magnesia raw material less than 50 mass% (excluding zero), and carbon raw material 50 mass%
Less than (not including zero), a binder is externally added in a range of 0.1 to 20% by mass, kneading, molding,
A molded article obtained by drying or firing in a non-oxidizing atmosphere or without firing, and comprising a spinel-containing refractory molded article having an inevitable impurity amount of 15% by mass or less in the molded article. A refractory for a converter tapping outlet (hereinafter referred to as a "fourth invention").

Further, the refractory for a converter tapping outlet of the present invention is
1, Si, Mg, Al-Mg alloy, Fe-Si alloy, B
₄ C, SiC, ZrC, ZrB ₂ , TiB ₂ , NbB ₂ , W
One or more additives selected from the group consisting of B, VB, BN, Si ₃ N ₄ , TiN and AlN are contained in an amount of 10% by mass or less on the basis of the weight of the composition. .

Further, the refractory for a converter outlet of the present invention is characterized in that it has been subjected to pitch impregnation treatment or tar impregnation treatment.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The refractory for a converter tap hole of the present invention adopts the following policy in order to improve its serviceability: to prevent oxidation of carbon raw material and dissolution into molten steel at the same time. The use of an appropriate amount of carbon material is also possible, and spalling resistance is easily obtained;
Obtaining improvement in corrosion resistance, spalling resistance and wear resistance by selecting an aggregate having low penetration of eO and MnO, a low coefficient of thermal expansion, and high strength and hardness.

Heretofore, few examples have examined the relationship between magnesia and the amount of FeO or MnO permeated. The present inventors have found that MgO.Al ₂ O ₃ -based spinel has higher F than magnesia.
It has been found that the permeation amount of eO and MnO is small. Spinel is an aggregate having a smaller expansion rate than magnesia, and high strength and hardness. Furthermore, the present inventors, when carbon is present in the tapping refractory of the present invention,
It has been found that when spinel and carbon raw material are used together, a dense layer of spinel of several μm to several hundred μm is formed on the working surface in contact with molten steel. That is, it was found that the dense layer of spinel became a protective layer, which prevented oxidation of carbon and dissolution in molten steel, and that the thin dense layer did not impair spalling resistance due to carbon. . Also, because the dense layer of this spinel is dense,
It was found that the abrasion resistance also increased. As described above, the combined use of spinel and carbon is not a mere combination, but exhibits a synergistic effect of increasing the effects of each other, indicating that it is a completely new technical knowledge that has never been seen before. When no carbon is present in the refractory for a converter tapping outlet of the present invention, no dense spinel layer is formed. However, in this case, the refractory for tapping holes does not originally contain carbon,
There is no need to worry about oxidation of carbon and dissolution in molten steel. That is, the above-described original properties of the spinel found by the present inventors are exhibited as they are.

Hereinafter, the refractory for a converter tap hole of the present invention will be described in detail. That is, the refractory for a converter tap hole according to the first invention of the present invention is a converter tap tap comprising a sleeve disposed in a converter tap section and a block disposed around the sleeve. A part or the whole of the refractory for mouth is 100% by mass of a spinel raw material whose main components are magnesia and alumina,
A molded article obtained by adding, kneading, molding, and drying a binder in a range of 0.1 to 20% by mass on the outer surface and calcining or not calcining in a non-oxidizing atmosphere; Is characterized by being constituted by a spinel-containing refractory molded body having an unavoidable impurity amount of 15% by mass or less.

Here, the spinel raw material whose main component is magnesia-alumina used in the present invention may be an electrofused product or a sintered product. In addition, magnesia coexistence type,
Either an alumina-excess type spinel or a theoretical composition type spinel may be used, but desirably, magnesia is 20 to 30% by mass, preferably 24 to 29% by mass, and alumina is 70 to 80% by mass, preferably 71 to 76% by mass. A spinel of a theoretical composition type having a composition and having an unavoidable impurity of 3.0% by mass or less, preferably 1.5% by mass or less is good. It is not preferable that the composition deviates from the composition of the theoretical composition type spinel because the corrosion resistance and the heat spalling resistance are inferior.

In the spinel raw material whose main components are magnesia and alumina, coarse particles having a particle size of 1 mm or more are 20% by mass or more, preferably 25% by mass or more, and most preferably 30 to 7%.
Those containing in an amount of 0% by mass are preferred. Here, if the spinel raw material has less than 20% by mass of coarse particles having a particle diameter of 1 mm or more, the spalling resistance is undesirably reduced.

The binder used in the first invention of the present invention is a group consisting of phenol resin, epoxy resin, furan resin, acrylic resin, silicone resin, polyvinyl alcohol, tar, pitch, bitter and molasses which are usually used. One or two or more selected from Here, the compounding amount of the binder is 0.1 to 20% by mass, preferably 0.1 to 1%, based on 100% by mass of the spinel raw material.
It is within the range of 0% by mass. If the amount of the binder is less than 0.1% by mass, there is no effect of adding the binder, and the molded body cannot be maintained, which is not preferable. In addition, the compounding amount is 20
If the amount exceeds 50% by mass, a large amount and large pores are generated after the volatile matter in the binder is released during the drying step and the baking step of the molded body and during heating during use, and the molded body has reduced strength, oxidation, and molten steel intrusion. Etc. are not preferred.

The compound having the above-described compounding ratio is kneaded to obtain a kneaded soil. For kneading, a normal wet pan,
A mixer such as a universal mixer, an Erich mixer, a planetary mixer, a kneader mixer, a high-speed mixer, an omni mixer, or the like can be used. The obtained kneaded soil (kneaded material) is usually used in an oil press,
It is formed into a predetermined shape using a press machine such as a friction press or an isostatic press. At that time, deaeration (vacuum treatment) may be performed for the purpose of removing air from the kneaded material. The obtained molded body is used for the purpose of curing treatment of the binder and / or removing volatile components in the binder.
It is dried in the range of 0 to 300 ° C., preferably 150 to 250 ° C. to obtain an unfired product, or after drying, is a non-oxidizing atmosphere at a temperature of 600 ° C. or more, preferably 800 to 1400 ° C. It is fired in a fired product.

Further, a tar impregnation treatment or a pitch impregnation treatment can be performed as required. The impregnating treatment can be performed by charging the dried or calcined product into a tar or pitch melting tank set at a predetermined temperature in the range of 100 to 600 ° C., preferably 150 to 500 ° C. in advance. Alternatively, the impregnation treatment may be performed after the deaeration treatment for removing air from the dried product or the fired product. Also,
The impregnating step and the drying and firing steps may be repeated a plurality of times. 600 ° C. or less after impregnation, preferably 100 to 4
It is also possible to dry at 00 ° C. to remove volatiles in tar or pitch. The processing required for obtaining the final shape can be performed after molding and drying, or may be performed after firing or impregnation.

In producing a refractory such as a refractory for a converter tapping outlet according to the first invention of the present invention, the raw material is a natural raw material such as a natural mineral or clay, or a raw material manufactured from the same. Usually, artificial raw materials are used, and thus, the molded body obtained as described above may contain unavoidable impurities derived from these raw materials. Inevitable impurities, due to their components, cause corrosion resistance, spalling resistance, abrasion resistance, oxidation resistance,
The proportion is 15% by mass or less (including zero), preferably 10% by mass or less (including zero), more preferably 5% by mass or less (including zero). If the amount of inevitable impurities exceeds 15% by mass, the above-mentioned properties are deteriorated, and it is not possible to improve the durability of the refractory for a converter outlet. Here, as the inevitable impurities, CaO, SiO ₂ , A
l ₂ O ₃ , MgO, Cr ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , Ti
O ₂ , FeO, MnO, Fe ₂ O ₃ , CeO, Na ₂ O, K
Oxides such as ₂ O and B ₂ O ₃ or composite oxides thereof are exemplified.

The refractory for a converter tapping outlet of the first invention of the present invention includes Al, Si, Mg, an Al-Mg alloy, Fe-
Si alloy, B ₄ C, SiC, ZrC, ZrB ₂ , Ti
B ₂ , MgB ₂ , NbB ₂ , WB, VB, BN, Si
One or more additives selected from the group consisting of ₃ N ₄ , TiN and AlN are externally added in an amount of 20% by mass or less (excluding zero), preferably 10% by mass or less (excluding zero). Can be blended. These components act to prevent oxidation of the refractory and improve the strength. Here, if the compounding amount of these components exceeds 20% by mass, the effect of the spinel raw material is not exhibited, and it is not preferable because the durability cannot be expected to be improved.

Next, the refractory for a converter tapping port according to the second invention of the present invention comprises a sleeve disposed on the converter tapping portion and a block disposed around the sleeve. A part or the whole of the refractory for a converter tapping hole is composed of 50% by mass or more of spinel raw material whose main component is magnesia and alumina.
0.1% by weight of the binder was added to the blend consisting of less than 0% by mass and 50% by mass or less (not including zero) of the carbon raw material.
A molded body obtained by adding, kneading, molding and drying in a range of ２０20% by mass and then calcining or non-firing in a non-oxidizing atmosphere, and the amount of inevitable impurities of the molded body is 15% by mass.
It is characterized by comprising the following spinel-containing refractory molded body.

Here, the spinel raw materials whose main components are magnesia and alumina used in the second invention of the present invention are the same as the spinel raw materials used in the first invention.

The carbon raw material used in the second invention of the present invention includes natural graphite, earthy graphite, artificial graphite, coke, anthracite, quiche graphite, pitch charcoal, tar charcoal, treated graphite, electrode scrap, charcoal heat Decomposed graphite, carbon black,
Examples thereof include recrystallized graphite, amorphous carbon, and resin charcoal, and one or more of these can be used in combination.

In the spinel-containing refractory compact used in the converter refractory for a steel tapping outlet of the present invention, the mixing ratio of the spinel raw material and the carbon raw material is 50% by mass or more and less than 100% by mass of the spinel raw material and 50% by mass or less. It is within the range of not more than 35% by mass (not including zero), preferably not more than 35% by mass (not including zero). Here, the mixing ratio of the spinel raw material is 50% by mass or less, that is, the mixing ratio of the carbon raw material is 5%.
If the content exceeds 0% by mass, the characteristics as a spinel refractory are reduced, which is not preferable.

The binder used in the second invention of the present invention is the same as that used in the first invention.

The refractory for a converter tapping port according to the second invention of the present invention can be manufactured substantially in the same manner as the first invention. Also, various additives can be blended in the same manner as in the first invention. Further, a tar impregnation treatment or a pitch impregnation treatment can be performed as necessary.

Here, when producing a refractory such as a refractory for a converter tapping outlet according to the second invention of the present invention, as in the first invention, the raw material is a material such as a natural mineral or clay. It is common to use natural raw materials or artificial raw materials produced therefrom, and thus the obtained molded body may contain unavoidable impurities derived from these raw materials. The unavoidable impurities cause the components to reduce the corrosion resistance, spalling resistance, abrasion resistance, and oxidation resistance due to their components. Therefore, the proportion is 15% by mass or less (including zero), preferably 10% by mass or less ( And more preferably 5% by mass or less (including zero). When the amount of inevitable impurities exceeds 15% by mass, the above-mentioned characteristics are deteriorated,
It is not possible to improve the service life of refractories for converter tapping outlets. here,
The unavoidable impurities include CaO, SiO ₂ , MgO, Al ₂ O ₃ ,
r ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , TiO ₂ , FeO, MnO,
Oxides such as Fe ₂ O ₃ , CeO, Na ₂ O, K ₂ O, and B ₂ O ₃ , or composite oxides thereof, and the like can be given.

Next, the refractory for a converter tapping port according to the third invention of the present invention comprises a sleeve disposed on the converter tapping portion and a block disposed around the sleeve. A part or the whole of the refractory for a converter tapping hole is composed of 50% by mass or more of spinel raw material whose main component is magnesia and alumina.
For a composition consisting of less than 0% by mass and 50% by mass or less (not including zero) of a magnesia raw material, a binder is added to the outside by 0.1%.
A molded product obtained by adding, kneading, molding and drying in the range of 1 to 20% by mass and then calcining or not calcining in a non-oxidizing atmosphere, and the amount of unavoidable impurities of the molded body is 15% by mass. % Or less of the spinel-containing refractory molded body.

Here, the spinel raw materials whose main components are magnesia and alumina used in the third invention of the present invention are the same as the spinel raw materials used in the first invention.

The magnesia raw material used in the present invention can be exemplified by calcined clinker such as natural magnesite, seawater magnesia, and sweet water magnesia.

In the spinel-containing refractory molded product used in the converter refractory for a steel tapping outlet of the present invention, the mixing ratio of the spinel raw material and the magnesia raw material is 50 mass% of the spinel raw material.
It is in the range of not less than 100% by mass and not more than 50% by mass (not including zero) of the magnesia raw material, preferably not more than 35% by mass (not including zero). Here, when the blending ratio of the spinel raw material is less than 50% by mass, that is, the blending ratio of the magnesia raw material exceeds 50% by mass, the characteristics of the spinel refractory are undesirably reduced.

The binder used in the third invention of the present invention is the same as that used in the first invention.

The refractory for a converter tapping port according to the third invention of the present invention can be manufactured substantially in the same manner as the first invention. Also, various additives can be blended in the same manner as in the first invention. Further, a tar impregnation treatment or a pitch impregnation treatment can be performed as necessary.

Here, when producing a refractory such as a refractory for a converter steel outlet according to the third invention of the present invention, as in the first invention, the raw material thereof may be natural minerals or clay. It is common to use natural raw materials or artificial raw materials produced therefrom, and thus the obtained molded body may contain unavoidable impurities derived from these raw materials. The unavoidable impurities cause the components to reduce the corrosion resistance, spalling resistance, abrasion resistance, and oxidation resistance due to their components. Therefore, the proportion is 15% by mass or less (including zero), preferably 10% by mass or less ( And more preferably 5% by mass or less (including zero). When the amount of inevitable impurities exceeds 15% by mass, the above-mentioned characteristics are deteriorated,
It is not possible to improve the service life of refractories for converter tapping outlets. here,
Inevitable impurities include CaO, SiO ₂ , Al ₂ O ₃ , and Cr, excluding the spinel material and the magnesia material.
₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , TiO ₂ , FeO, MnO, F
Oxides such as e ₂ O ₃ , CeO, Na ₂ O, K ₂ O, and B ₂ O ₃ , and composite oxides thereof are exemplified.

Next, a refractory for a converter tapping port according to a fourth aspect of the present invention comprises a sleeve disposed on a converter tapping portion and a block disposed around the sleeve. A part or the whole of the refractory for a converter tapping hole is composed of 50% by mass or more of spinel raw material whose main component is magnesia and alumina.
For a blend of less than 0% by mass, less than 50% by mass of magnesia raw material (not including zero) and less than 50% by mass of carbon raw material (not including zero), 0.1 to 2 binders are externally applied.
A molded product obtained by adding, kneading, molding and drying in a range of 0% by mass, and then calcining or not calcining in a non-oxidizing atmosphere, and the amount of inevitable impurities of the molded body is 15% by mass or less. And a spinel-containing refractory molded body.

Here, the spinel raw material whose main components are magnesia and alumina used in the fourth invention of the present invention is the same as the spinel raw material used in the first invention. The mixing ratio of the spinel material is 50% by mass or more and 10% by mass.
It is within the range of less than 0% by mass. If the blending ratio of the spinel raw material is less than 50% by mass, the characteristics as a spinel-based refractory decrease, which is not preferable.

The magnesia raw material used in the fourth invention of the present invention is also the same as the magnesia raw material used in the third invention. Incidentally, the mixing ratio of the magnesia raw material,
It is within the range of less than 50% by mass (excluding zero), preferably 35% by mass or less (excluding zero).

Further, the carbon raw material used in the fourth invention of the present invention is the same as the carbon raw material used in the second invention. The mixing ratio of the carbon raw material is less than 50% by mass (excluding zero), and preferably 35% by mass or less (excluding zero).

The binder used in the fourth invention of the present invention is the same as that used in the first invention.

The refractory for a converter tapping hole according to the fourth invention of the present invention can be manufactured substantially in the same manner as the first invention. Also, various additives can be blended in the same manner as in the first invention. Further, a tar impregnation treatment or a pitch impregnation treatment can be performed as necessary.

Here, when producing a refractory such as a refractory for a converter tapping outlet according to the fourth invention of the present invention, as in the first invention, the raw material is a material such as a natural mineral or clay. It is common to use natural raw materials or artificial raw materials produced therefrom, and thus the obtained molded body may contain unavoidable impurities derived from these raw materials. The unavoidable impurities cause the components to reduce the corrosion resistance, spalling resistance, abrasion resistance, and oxidation resistance due to their components. Therefore, the proportion is 15% by mass or less (including zero), preferably 10% by mass or less ( And more preferably 5% by mass or less (including zero). When the amount of inevitable impurities exceeds 15% by mass, the above-mentioned characteristics are deteriorated,
It is not possible to improve the service life of refractories for converter tapping outlets. here,
The impurities include CaO, SiO ₂ , Al ₂ except for the spinel material, magnesia material and carbon material.
O ₃ , Cr ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , TiO ₂ , FeO,
_{MnO, Fe 2 O 3, CeO} , Na 2 O, K 2 O, an oxide such as B ₂ O ₃ or a composite oxide thereof, and the like.

The first to fourth aspects of the present invention as described above
The distribution and material composition of the refractory for a converter tapping outlet according to the present invention can be performed as follows. That is, the sleeve and the block may be separately manufactured and combined at the time of use, or the sleeve and the block may be integrally formed in advance. Further, the sleeve may be made separately and combined at the time of use. Further, when combining the divided portions, the combination may be performed at a vacant joint, or may be performed using a joint material such as a mortar or a stamp material.

Further, an inner tube layer and an end layer having a certain thickness may be provided on the inner tube surface side of the sleeve which comes into contact with the molten steel and / or the slag and a part or all of the end surface sides of the sleeve and the block. The material of the inner tube layer and the end face layer can be different from the material of the inner main body layer. For example, the refractory for converter tapping outlet according to the first invention of the present invention is used for the inner tube layer and the end face layer, and the refractory for converter tapping exit according to the second invention of the present invention is used for the main body layer. And vice versa. Further, the refractory for a converter tapping outlet according to the fourth invention of the present invention is used for the inner tube layer and the end face layer, and the refractory for a converter tapping outlet according to the second invention of the present invention is used for the main body layer. And vice versa. Further, the refractory for a converter tapping outlet according to the first to fourth inventions of the present invention may be disposed on the inner tube layer and the end face layer, and another well-known refractory may be used for the main body layer. Other well-known refractories include, for example, oxide refractories such as fused silica, magnesia, alumina, cordierite, chamotte, and mullite, and oxides such as magnesia-carbon and alumina-carbon. Refractories combining silicon and carbon, or silicon carbide, carbides such as boron carbide, silicon nitride, nitrides such as aluminum nitride alone,
Alternatively, refractories in combination with oxides and carbon can be given.

FIG. 1 shows an example of a sleeve and a block constituting the refractory for a converter tap hole of the present invention. FIG.
Is a cross section in the molten steel passing direction and is a symmetrical figure with respect to the central axis. According to this embodiment, the cylindrical sleeve and the block are shown. However, in the present invention, the sleeve and the block are not limited to the cylindrical type, and may be a straight pipe, an elliptic pipe, or other shapes. It is not necessary that the sleeve and the block have the same shape. For example, the sleeve may have a cylindrical shape and the block may have a straight pipe shape. FIG.
Among them, 1 is an end face layer, 2 is a block, 3 is a working surface inside a converter, 4 is a sleeve, 5 is an inner tube layer, 6 is a split portion of a sleeve, 7 is a working surface of a sleeve bore, and 8 is a symmetrical surface. The central axis of the
Reference numeral 9 denotes a main body layer.

The thickness of the inner tube layer can be arbitrarily selected, but is preferably 80% or less, more preferably 50% or less of the total thickness of the main body layer and the inner tube layer. If the thickness exceeds 80%, the main body layer and the inner tube layer peel off, which is not desirable. Also, the thickness of the end face layer can be arbitrarily selected similarly, but the total thickness of the main body layer and the inner tube layer is 8%.
0% or less, preferably 50% or less. The thickness is 80
%, The main body layer and the inner tube layer peel off, which is not desirable.

The refractory for the converter tapping port of the present invention, which comprises a sleeve disposed in the converter tapping section and a block disposed around the sleeve, has a part or the whole thereof as described above. Although it is composed of a molded body obtained as described above, when the refractory contains carbon, when it comes into contact with molten steel, its working surface has a thickness of about several μm to several hundred μm. The formation of a dense spinel layer requires the presence of the above-mentioned spinel material in order to form the dense spinel layer. The dense layer of this spinel is relatively thin, several hundred μm from the refractory operation surface, and the refractory operation surface is the densest, gradually becoming sparse toward the back, and eventually leading to the original refractory structure Have.
Therefore, it does not peel off during use, but is firmly attached. In addition, the dense layer of spinel serves as a protective layer, preventing carbon pickup and simultaneously dissolving carbon in molten steel, preventing the refractory structure from becoming brittle, and preventing carbon oxidation. Also have.
Moreover, the spinel itself had very high erosion resistance to molten steel, and there was no damage to the refractory. If no carbon is present in the refractory for a converter tapping outlet of the present invention, a dense spinel layer is not formed. However, in this case, carbon is not originally present in the refractory for a converter tapping outlet, so there is no need to worry about oxidation of carbon and dissolution in molten steel, and the original characteristics of the spinel material are exhibited as it is. You.

[0061]

The present invention will be more specifically described below with reference to examples and comparative examples of the present invention. Examples Example 1 Table 1 below shows the compounding ratios of the materials of the product of the present invention and the comparative product. The specimens for measuring various properties were prepared by mixing the raw material blends described in Table 1 below with an oil press at 40 mm.
After forming into a shape of × 40 mm × 300 mm, and drying the obtained molded body at 200 ° C. for 24 hours, firing is performed under the conditions described in Table 1 (in a carbon breathe atmosphere). Those subjected to the impregnation treatment were obtained by performing the impregnation under the conditions shown in Table 1.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

[0068]

[Table 7]

[0069]

[Table 8]

[0070]

[Table 9]

[0071]

[Table 10]

[0072]

[Table 11]

[0073]

[Table 12]

[0074]

[Table 13]

[0075]

[Table 14]

[0076]

[Table 15]

[0077]

[Table 16]

[0078]

[Table 17]

[0079]

[Table 18]

[0080]

[Table 19]

[0081]

[Table 20]

[0082]

[Table 21]

[0083]

[Table 22]

In Table 1, the molten steel immersion experiment is an experiment performed using steel at the time of blowing off the converter. Under a non-oxidizing atmosphere (Ar gas), C = 0.06%, Mn = 0.25%, O = 5
A specimen (40 mm × 40 mm × 300 mm) was immersed in molten steel at 1700 ° C. having a component of 00 ppm for 1 minute, and the amount of carbon disappearance was measured. Separately, an experiment was conducted in which the specimen was immersed for 30 minutes, and MnO +
The amount of FeO permeation was measured. The amount of carbon disappearance was measured as the distance (mm) from the contact surface of the specimen with the molten steel in the range where carbon was lost, and was expressed as a ratio to the dimensions of the specimen. 0% indicates no carbon disappearance, and 100% indicates all carbon disappearance. Further, the penetration amount of MnO + FeO was determined by EPMA analysis at several places near the contact surface of the test piece with the molten steel, and was determined as the total amount of MnO and FeO. This indicates that the larger the amount of permeation, the more the property is deteriorated.

The erosion test was conducted by using the molten steel and CaO / SiO ₂
Mass ratio = 3.7, MnO = 5.0%, T.O. Fe (total F
e) = Conversion furnace slag having a component of 18% was used. After immersing the specimen (40 mm × 40 mm × 300 mm) for 1 hour, the erosion depth of the specimen and, when a dense layer was formed, the average thickness (μm) thereof were measured. The erosion resistance is a value obtained by dividing the value obtained by subtracting the erosion depth from the specimen size by the specimen size. 100% indicates high erosion resistance, and 0% is completely eroded. Indicates that the specimen has disappeared. The dense layers formed in the product of the present invention were all spinel dense layers.

The spalling resistance of the test piece (40 mm ×
(40 mm × 300 mm) is immersed in hot metal at 1650 ° C. and subjected to a thermal shock. The change in elastic modulus of the sample before and after immersion is indexed. The ratio of the elastic modulus after immersion to the elastic modulus before immersion was expressed as a percentage. 100% indicates high spalling resistance, 0% indicates low spalling resistance,
If it is less than 0%, the sample has many cracks, and it is practically impossible to measure the elastic modulus.

The oxidation resistance is obtained by indexing the depth of carbon disappearance from the heating surface with respect to the sample size when the specimen after the molten steel immersion test was heated in an air atmosphere at 1500 ° C. for one hour. At 100%, the oxidation resistance is the highest and is 0%.
% Indicates that the carbon has completely disappeared. In addition,
Abrasion resistance can be evaluated by strength characteristics. That is, the higher the strength, the higher the wear resistance.

Next, Table 2 below shows the distribution, material composition and use results when the refractories for converter tapping outlets of the present invention product and the comparative product shown in Table 1 are applied to an actual machine.

[0089]

[Table 23]

[0090]

[Table 24]

[0091]

[Table 25]

[0092]

[Table 26]

[0093]

[Table 27]

[0094]

[Table 28]

[0095]

[Table 29]

[0096]

[Table 30]

[0097]

[Table 31]

In the method of combining the sleeve and the block shown in Table 2, the term “integral method” refers to the case of using a refractory manufactured by integrally molding the sleeve and the block, and the term “joining method” refers to the method of separately manufacturing the sleeve and the block. Then, the case where both are joined and used by using a mortar at the time of actual machine distribution is shown. Further, in the sleeve structure, the divided structure refers to a case where a divided and manufactured sleeve is used by joining the divided parts using a mortar at the time of actual machine delivery as shown in FIG. Here, a case is shown in which the same size as that used in the actual machine is manufactured and used as it is. The inner tube layer and the end face layer show the parts shown in FIG. 1, and the materials applied to each are shown using the numbers in Table 1. Further, the body layer material, MgO-C protein has a composition obtained by adding 2 wt% metallic Al outside multiplying the formulation of 80 wt% carbon 20 wt% magnesia, Al ₂ O ₃ -C quality is SiC is added to a blend of 80% by mass of alumina and 20% by mass of carbon,
The cordierite has a composition of cordierite 90% by mass and magnesia 10% by mass, and the mullite has a composition of mullite 90% by mass and alumina 10% by mass.
Has the composition by weight%, SiC matter has a composition of metal Si powder was added outside hanging 3 wt% with respect to silicon carbide, Si ₃
The N ₄ material has a composition in which 5% by mass of metal Si powder is externally added to silicon nitride, and the MgO material has a composition in which 5% by mass of CaO is externally added to magnesia. The material has a composition of 100% by mass of fused silica,
The N material has a composition of 100% by mass of aluminum nitride.

In the actual machine use evaluation test shown in Table 2, the service charge increase rate is the increase rate when the number of charges up to the start of the repair is the service charge number of the tapping sleeve and block, and the reference comparison product is used as a reference. The larger the value, the better. The repair frequency is obtained by calculating the number of repairs per charge and expressing the ratio to the number of repairs of the regular article as a percentage. 100% indicates the number of repairs equivalent to that of ordinary products, and the smaller the numerical value, the smaller the number of repairs and the better. The frequency of replacement was calculated by dividing the number of times the tapping sleeve and block were replaced until the converter body reached the serviceable limit by the number of serviceable charges of the converter body, and expressed as an index based on ordinary products. Things. 100% represents a replacement frequency equivalent to that of a common product, and a smaller value indicates that the replacement frequency is smaller and better. In addition, the reference comparative product in Table 2 shows a comparative example in which the method of combining the present invention product with the sleeve and the block, the sleeve structure and the presence or absence of the inner tube layer, the end face layer, the main body layer, and the like are substantially the same. is there.

[0100]

As described above, the refractory for a converter tapping outlet according to the first to fourth inventions of the present invention has the spinel raw material itself having FeO, MnO penetration resistance, corrosion resistance, and spalling resistance. In addition to being high, it has a feature of forming a dense layer of spinel, and thus has an effect of suppressing oxidation of carbon and dissolution in molten steel. Therefore, compared with the conventional magnesia-carbon refractory, it is possible to realize a great improvement in service life, a great reduction in the frequency of repair and replacement, and contribute to an improvement in the operation rate of the converter.

[Brief description of the drawings]

FIG. 1 is a view showing an example of a sleeve and a block constituting a refractory for a converter tapping outlet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 End face layer 2 Tap hole block 3 Operating surface inside converter 4 Tap tap sleeve 5 Inner pipe layer 6 Split section of tap tap sleeve 7 Working face of tap hole inner hole 8 Symmetric center axis 9 Main body layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhiro Hoshiyama 4-7-1 Kudankita, Chiyoda-ku, Tokyo Shinagawa Kawabashi Brick Co., Ltd. (72) Inventor Hayashi ▲ Wei ▼ 4-chome, Kudankita, Chiyoda-ku, Tokyo No.1-7 Product Kawashira Brick Co., Ltd. F term (reference) 4G033 AA02 AA03 AA09 AA14 AB09 AB10 AB25 4K002 BD01

Claims (9)

[Claims] 1. A part or the whole of a refractory for a converter tapping port, which is composed of a sleeve disposed on a converter tapping portion and a block disposed around the sleeve, is mainly composed of magnesia. And a binder is added in a range of 0.1 to 20% by mass with respect to 100% by mass of a spinel raw material that is alumina,
A spinel-containing refractory molded article obtained by kneading, molding, drying, and calcining or not calcining in a non-oxidizing atmosphere, wherein the molded article has an unavoidable impurity amount of 15% by mass or less. A refractory for a converter tapping outlet, characterized by comprising: 2. A part or whole of a refractory for a converter tapping port, which is composed of a sleeve disposed in a converter tapping portion and a block disposed around the sleeve, is mainly composed of magnesia. And 50% by mass or more of spinel material as alumina
For a blend consisting of less than 00% by weight and 50% by weight or less (not including zero) of a carbon raw material, a binder is added at an external rate of 0.1%.
A molded product obtained by adding, kneading, molding and drying in the range of 1 to 20% by mass and then calcining or not calcining in a non-oxidizing atmosphere, and the amount of unavoidable impurities of the molded body is 15% by mass. % Or less, comprising a spinel-containing refractory molded body having a content of not more than 0.1%. 3. A part or whole of a refractory for a converter tapping port, which is composed of a sleeve disposed in a converter tapping portion and a block disposed around the sleeve, is mainly composed of magnesia. And 50% by mass or more of spinel material as alumina
To a composition consisting of less than 00% by mass and less than 50% by mass of magnesia raw material (excluding zero), a binder is externally added in a range of 0.1 to 20% by mass, kneaded, molded, dried and then non-oxidized. A molded article obtained by firing or not firing in a neutral atmosphere, wherein the amount of unavoidable impurities of the molded article is 1
A refractory for a converter tapping outlet, comprising a spinel-containing refractory molded body of 5% by mass or less. 4. A part or the whole of a refractory for a converter tap hole, which is composed of a sleeve disposed in a converter tapping portion and a block disposed around the sleeve, is mainly composed of magnesia. And 50% by mass or more of spinel material as alumina
For a composition consisting of less than 00% by mass, less than 50% by mass of magnesia raw material (not including zero) and less than 50% by mass of carbon raw material (not including zero), 0.1 to 100% of binder is externally applied.
A molded product obtained by adding, kneading, molding and drying in a range of 20% by mass and then calcining or not calcining in a non-oxidizing atmosphere, and the amount of inevitable impurities of the molded body is 15% by mass or less. A refractory for a converter tapping outlet, comprising a spinel-containing refractory molded body as described above. 5. The refractory for a steel exit of a converter according to claim 1, wherein the spinel raw material whose main components are magnesia and alumina contains 20% by mass or more of coarse particles having a particle size of 1 mm or more. 6. The refractory for a converter steel outlet according to claim 3, wherein the spinel raw material and the magnesia raw material whose main components are magnesia and alumina contain 20% by mass or more of coarse particles having a particle size of 1 mm or more. . 7. The spinel raw material whose main component is magnesia and alumina is a theoretical composition type spinel raw material in which magnesia is 20 to 30% by mass, alumina is 70 to 80% by mass, and an unavoidable impurity amount is 3.0% by mass or less. The refractory for a converter tapping hole according to any one of claims 1 to 6. 8. Al, Si, Mg, Al-Mg alloy, F
e-Si alloy, B_FourC, SiC, ZrC, ZrB_Two, Ti
B_Two, NbB_Two, WB, VB, BN, Si_ThreeN _Four, TiN and
Or two or more selected from the group consisting of
In an amount of not more than 10% by mass based on the formulation.
The steel tapping hole of the converter according to any one of claims 1 to 7.
For refractories. 9. The refractory for a converter tapping outlet according to claim 1, which has been subjected to pitch impregnation treatment or tar impregnation treatment.