CN115043645A - Long-service-life continuous casting tundish dry material and preparation method thereof - Google Patents
Long-service-life continuous casting tundish dry material and preparation method thereof Download PDFInfo
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
- C04B35/6316—Binders based on silicon compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/401—Alkaline earth metals
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—Aluminium
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
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Abstract
The invention relates to a tundish dry material, in particular to a high-service-life continuous casting tundish dry material and a preparation method thereof. The preparation raw materials of the tundish dry material comprise, by weight, magnesia, a bonding agent, a bonding accelerator and an antioxidant. According to the invention, the silicon binder and the saccharide binder act together, and particularly, the hydrous metasilicate and the sucrose are used together as the binders, so that the problems of pollution prevention, environmental protection improvement, stability of molding and demolding, paste and the like are also promoted. By using the combined action of the magnesia, the bonding agent, the bonding accelerator and the antioxidant, the corrosion resistance and the processing performance can be improved, the service life of the tundish is prolonged, simultaneously, the phenomena of recarburization and steel enhancement on molten steel caused by carbon residue of the carbohydrate bonding agent and the like are avoided, the formed steel has smooth surface and no problems of holes and the like, and the method can be used for processing low-carbon steel and the like.
Description
Technical Field
The invention relates to a tundish dry material, in particular to a high-service-life continuous casting tundish dry material and a preparation method thereof.
Background
The tundish dry material is used as an important refractory material for a tundish working lining in the steel continuous casting industry, and has important influence on preparing high-performance and high-quality steel. The tundish can be continuously flushed by molten steel and impacted by steel slag in the using process, and the service life of the tundish dry material can be influenced, so that the continuous casting industry is influenced.
CN108178641A provides a tundish dry material and a preparation method thereof, the tundish dry material is obtained by magnesia powder, wustite powder, carbonaceous binder and additive, and has the advantages of low production cost, high sintering activity of the product, long service life and the like.
However, since carbonaceous binders, especially carbohydrate binders, are decomposed at a relatively low temperature, which may cause problems such as mush in the preparation process and affect the corrosion resistance and service life at a medium temperature, a new tundish dry material is required to be provided to improve the processing and service performance.
Disclosure of Invention
In order to solve the problems, the invention provides a high-service-life continuous casting tundish dry material, which comprises 90-95 parts by weight of magnesia, 5-10 parts by weight of a bonding agent, 5-10 parts by weight of a bonding accelerator and 1-3 parts by weight of an antioxidant.
Magnesite clinker
In one embodiment, the magnesite according to the invention is fused magnesite and/or sintered magnesite. The particle size of the magnesia is 0.05-5 mm. The particle size of the magnesia is within 0.05-5 mm, and the specific particle size distribution is not particularly limited.
Binding agents
In one embodiment, the binding agent of the present invention comprises a carbohydrate binding agent selected from one or more of sucrose, fructose, lactose, galactose.
Preferably, the binding agent further comprises a silicon-based binding agent, wherein the silicon-based binding agent comprises one or more of metasilicate, magnesium aluminum silicate and silicate.
More preferably, the weight ratio of the carbohydrate binder to the silicon binder is 1: (0.5 to 1.5).
Further preferably, the metasilicate of the present invention is selected from one or more of anhydrous metasilicate, pentahydrate metasilicate, and nonahydrate metasilicate. Such as sodium metasilicate.
The carbohydrate binder is used as an environment-friendly binder, so that the environmental pollution in the preparation and use processes of the tundish can be avoided, but the inventor finds that caramel is easily formed and even further carbonized during low-temperature sintering molding in the preparation process of the carbohydrate binder, particularly cane sugar and the like, so that the problems of paste and the like are caused.
The inventor surprisingly finds that by using the combined action of the silicon-based binder and the carbohydrate binder, particularly the combined action of the hydrous metasilicate and the cane sugar as the binder, the pollution is avoided, the environmental protection is improved, meanwhile, the stability of forming and demoulding is promoted, and the problems of fuzzy forming and the like are avoided.
This is probably because by using a hydrous metasilicate, on the one hand, the metasilicate and sucrose act together under the action of water to form a gel system, and on the other hand, the metasilicate and gel system structure shrinks along with the volatilization of water and the formation of caramel or other carbides, so that the metasilicate is covered around the caramel and the like, and the action with a mold is avoided, thereby promoting the stability of mold release.
Furthermore, the inventors found that the nonahydrate metasilicate more readily promoted stabilization of the molding and demolding than the pentahydrate metasilicate structure, probably because the greater binding of the metasilicate promoted the formation of a more uniform gel system and the coverage of the metasilicate.
Binding promoters
In one embodiment, the bonding promoter of the present invention is selected from one or more of clay, diatomaceous earth, kaolin.
Preferably, the particle size of the kaolin is 100-300 μm. The particle size of the kaolin is between 100 and 300 mu m, and the specific particle size distribution is not particularly limited.
More preferably, the kaolin of the present invention comprises hard kaolin and soft kaolin, and the weight ratio of the hard kaolin to the soft kaolin is 1: (3-4).
The inventor finds that the addition of the hydrous metasilicate is beneficial to demolding and forming, but the volatilization of more water also leads to loose structure during the medium-temperature use process and is easy to cause the corrosion of steel slag, and the inventor surprisingly finds that the improvement of corrosion resistance, especially long-term corrosion resistance and service life can be promoted by using kaolin, especially hard kaolin and soft kaolin together.
The inventors have found that this is probably due to the fact that on the one hand the kaolin lamellar structure, in particular the more open porous crystalline structure of the soft kaolin, defines the path for water evaporation, reduces the number and size of pores and reduces the apparent porosity, and on the other hand the less amorphous, dense, hard kaolin is adsorbed around the soft kaolin, supporting the structure of the soft kaolin, even because of its denser texture, entering the interior of the soft kaolin and metasilicates, further modifying the dense structure of the surface layer of the tundish, avoiding penetration and further erosion of the steel slag.
Furthermore, the inventors have found that it is necessary to control the amount of soft kaolin and hard kaolin, and that it is difficult to define and guide the number and size of pores when the hard kaolin is high, so that the surface structure of the tundish is more open and adversely affects the erosion resistance.
Antioxidant agent
In one embodiment, the antioxidant is selected from one or more of silicon powder, magnesium powder and aluminum powder.
Preferably, the antioxidant is a nano antioxidant.
The inventor finds that although more soft kaolin improves the corrosion resistance, the more soft kaolin has a porous structure, the more soft kaolin also influences the increase of the volume density in the middle-temperature calcination process, is difficult to form a high-density tundish and influences the pressure resistance and the bending resistance, and the inventor surprisingly finds that the use of the nano antioxidant, especially the nano aluminum powder, is beneficial to promoting the further improvement of the corrosion resistance and obtaining a more compact structure.
The reason is probably that the nano aluminum oxide is used, the surface performance and the small particle size of the nano aluminum powder are utilized, the nano aluminum powder is favorable for entering kaolin, especially the inside of porous soft kaolin, and the nano aluminum powder is subjected to volume expansion to form aluminum oxide and the like during the forming process, so that gaps of the kaolin can be partially filled, and the nano aluminum oxide can act with silicon-oxygen tetrahedron and aluminum-oxygen-hydrogen octahedron crystal structures of the kaolin, so that the crystal structures of the soft kaolin are rearranged, the compactness of the kaolin is further promoted, and oxides of magnesium and the like in magnesia are further subjected to solid solution combination with a binding agent, an antioxidant and a binding accelerator along with the medium temperature, and the improvement of the volume density and the corrosion resistance is promoted.
Furthermore, the inventors have found that the amount of the antioxidant to be used needs to be controlled, and when the amount of the antioxidant is large, the limitation of the pore structure and the number of kaolin pores is easily affected, thereby adversely affecting the corrosion resistance.
The invention provides a preparation method of the long-life continuous casting tundish dry material, which comprises the following steps: and (3) blending magnesia, a bonding agent, a bonding accelerator and an antioxidant, sintering and demolding to obtain the tundish dry material.
The inventor finds that the combined action of the magnesia, the bonding agent, the bonding accelerator and the antioxidant can improve the corrosion resistance and the processing performance, promote the service life of the tundish to be prolonged, simultaneously is beneficial to avoiding the phenomena of recarburization and steel increment of molten steel caused by residual carbon of the carbohydrate bonding agent and the like, and the formed steel has smooth surface and no problems of holes and the like and can be used for processing low-carbon steel and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the silicon binder and the saccharide binder act together, and particularly, the hydrous metasilicate and the sucrose are used together as the binders, so that the problems of pollution prevention, environmental protection improvement, stability of molding and demolding, paste and the like are also promoted.
(2) The inventors have found that the use of kaolin, especially hard kaolin and soft kaolin, promotes improved corrosion resistance, especially long term corrosion resistance, and improved life.
(3) The inventors have found that the use of a nano antioxidant, particularly a nano aluminum powder, contributes to further improvement in corrosion resistance and the achievement of a more compact structure.
(4) By using the combined action of the magnesia, the bonding agent, the bonding accelerator and the antioxidant, the corrosion resistance and the processing performance can be improved, the service life of the tundish is prolonged, simultaneously, the phenomena of recarburization and steel increment on molten steel caused by residual carbon of the carbohydrate bonding agent and the like are avoided, the formed steel has smooth surface and no problems of holes and the like, and the method can be used for processing low-carbon steel and the like.
Detailed Description
Examples
Example 1
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia and 8 parts of a bonding agent by weight of preparation raw materials; the binding agent is sucrose.
The present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia and a bonding agent, sintering at 300 ℃ for 3 hours, forming, and demolding to obtain the tundish dry material.
Example 2
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia and 8 parts of a bonding agent by weight of preparation raw materials; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1.
the present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia and a bonding agent, sintering at 300 ℃ for 3h for molding, and demolding to obtain the tundish dry material.
Example 3
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia, 8 parts of a bonding agent and 6 parts of kaolin by weight; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1, the particle size of the kaolin is 100-300 μm, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: 3.5.
the present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia, a bonding agent and kaolin, sintering for 3 hours at 300 ℃, forming and demolding to obtain the tundish dry material.
Example 4
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia, 8 parts of a bonding agent, 6 parts of kaolin and 2 parts of an antioxidant by weight; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1, the particle size of the kaolin is 100-300 μm, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: 3.5, the antioxidant is nano aluminum powder.
This example provides a method for producing a long-life continuous casting tundish dry material as described above, including: and (3) blending magnesia, a bonding agent, kaolin and an antioxidant, sintering for 3 hours at 300 ℃, forming and demolding to obtain the dry tundish material.
Example 5
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises the following raw materials, by weight, 95 parts of magnesia, 9 parts of a bonding agent, 8 parts of kaolin and 3 parts of an antioxidant; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1.2, the particle size of the kaolin is 100-300 μm, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: 4, the antioxidant is nano aluminum powder.
The present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia, a bonding agent, kaolin and an antioxidant, sintering for 3 hours at 300 ℃, forming and demolding to obtain the dry tundish material.
Example 6
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 90 parts of magnesia, 5 parts of a bonding agent, 5 parts of kaolin and 1 part of an antioxidant by weight; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 0.5, the particle size of the kaolin is 100-300 μm, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: 3, the antioxidant is nano aluminum powder.
The present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia, a bonding agent, kaolin and an antioxidant, sintering for 3 hours at 300 ℃, forming and demolding to obtain the dry tundish material.
Example 7
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia, 8 parts of a bonding agent and 6 parts of kaolin by weight; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1, the particle size of the kaolin is 100-300 μm, and the kaolin comprises soft kaolin.
This example provides a method for producing a long-life continuous casting tundish dry material as described above, including: and (3) blending magnesia, a bonding agent and kaolin, sintering for 3 hours at 300 ℃, forming and demolding to obtain the tundish dry material.
Example 8
The embodiment provides a long-service-life continuous casting tundish dry material, which comprises 92 parts of magnesia, 8 parts of a bonding agent, 6 parts of kaolin and 2 parts of an antioxidant by weight; the binding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1: 1, the particle size of the kaolin is 100-300 μm, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: 3.5, wherein the antioxidant is submicron aluminum powder.
The present embodiment provides a method for preparing a long-life continuous casting tundish dry material, including: and (3) blending magnesia, a bonding agent, kaolin and an antioxidant, sintering for 3 hours at 300 ℃, forming and demolding to obtain the dry tundish material.
Evaluation of Performance
1. Paste-blur Property: and (3) observing whether the problem of fuzzy is existed in the processes of sintering at 300 ℃ for 3 hours and forming and demolding, wherein the 1 grade is continuous 10 times of sintering and forming without fuzzy, the 2 grade is continuous 8-9 times of sintering and forming without fuzzy, the 3 grade is continuous 6-7 times of sintering and forming without fuzzy, and the 4 grade is continuous within 5 times of sintering and forming without fuzzy, and the result is shown in table 1.
2. Corrosion resistance: sintering at 300 ℃ for 3h for forming to obtain a hollow cylindrical sample, and carrying out corrosion resistance test on the hollow cylindrical sample, wherein steel slag (containing 6% of metallic iron, 50% of calcium oxide, 8% of magnesium oxide and 6% of manganese oxide) is added into the sample, and after the sample is heated to 1500 ℃ and sintered for 3h, 6h and 9h, the depth of the bottom of the sample corroded by the steel slag is tested, wherein the depth of the grade 1 is less than 3mm, the depth of the grade 2 is less than or equal to 5mm and greater than 3mm, the depth of the grade 3 is less than 8mm and greater than 5mm, the depth of the grade 4 is less than or equal to 12mm and greater than 8mm, the depth of the grade 5 is less than or equal to 16mm and greater than 12mm, the depth of the grade 6 is less than or equal to 20mm and greater than 16mm, and the depth of the grade 7 is greater than 20mm, and the results are shown in Table 1.
3. Bulk density: sintering at 300 deg.C for 3h for molding, sintering at 1500 deg.C for 3h, and testing volume density according to GB T4513.6, wherein the volume density of grade 1 is greater than 2.6g/cm 3 2 grade is that the volume density is less than or equal to 2.6g/cm 3 Greater than 2.4g/cm 3 The 3-grade is that the volume density is less than or equal to 2.4g/cm 3 Greater than 2.2g/cm 3 The 4-grade is that the volume density is less than or equal to 2.2g/cm 3 The results are shown in Table 1.
Table 1 performance characterization test
According to the test results, the tundish dry material provided by the invention can be used for steel continuous casting, has a long service life, and does not introduce impurities into steel.
Claims (10)
1. The long-service-life continuous casting tundish dry material is characterized by comprising 90-95 parts by weight of magnesia, 5-10 parts by weight of a bonding agent, 5-10 parts by weight of a bonding promoter and 1-3 parts by weight of an antioxidant.
2. The high life continuous casting tundish dry material according to claim 1, wherein the binder comprises a sugar binder selected from one or more of sucrose, fructose, lactose, galactose.
3. The long-life continuous casting tundish dry material according to claim 2, wherein the binder further comprises a silicon-based binder, the silicon-based binder comprising one or more of metasilicate, magnesium aluminum silicate, and silicate.
4. The long-life continuous casting tundish dry material according to claim 3, wherein the weight ratio of the sugar binder to the silicon binder is 1: (0.5 to 1.5).
5. The long-life continuous casting tundish dry material according to claim 3, wherein the metasilicate is selected from one or more of anhydrous metasilicate, pentahydrate metasilicate, and nonahydrate metasilicate.
6. The long-life continuous casting tundish dry material according to claim 1, wherein the bonding promoter is selected from one or more of clay, diatomite and kaolin.
7. The long-life continuous casting tundish dry material according to claim 6, wherein the particle size of the kaolin is 100-300 μm.
8. The long-life continuous casting tundish dry material according to claim 6, wherein the kaolin comprises hard kaolin and soft kaolin, and the weight ratio of the hard kaolin to the soft kaolin is 1: (3-4).
9. The long-life dry material for the continuous casting tundish according to any one of claims 1 to 8, wherein the antioxidant is selected from one or more of silicon powder, magnesium powder and aluminum powder.
10. The method for preparing the long-life continuous casting tundish dry material according to any one of claims 1 to 9, characterized by comprising the following steps: and (3) blending magnesia, a bonding agent, a bonding accelerator and an antioxidant, sintering and demolding to obtain the tundish dry material.
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