CN115043645B - 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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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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 long-service-life continuous casting tundish dry material and a preparation method thereof. The tundish dry material is prepared from the following raw materials in parts by weight, such as magnesia, a binding agent, a binding promoter and an antioxidant. The invention uses the combined action of the silicon binding agent and the saccharide binding agent, especially the combined action of the hydrous metasilicate and the sucrose as the binding agent, thereby avoiding pollution, improving the environmental protection, simultaneously promoting the stability of molding and demolding, avoiding the problems of sticking and the like. By using the combined action of the magnesia, the binding agent, the binding promoter and the antioxidant, the corrosion resistance and the processing performance can be improved, the service life of the tundish is prolonged, the phenomenon of carburetion and steel increment of molten steel caused by carbon residue of a carbohydrate binding agent and the like can be avoided, the formed steel has smooth surface and no hole and the like, and the invention 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 long-service-life continuous casting tundish dry material and a preparation method thereof.
Background
The tundish dry material is used as a refractory material for a tundish working lining important in the steel continuous casting industry, and has important influence on preparing high-performance and high-quality steel. The tundish is continuously flushed by molten steel and impacted by steel slag in the using process, so that the service life of the tundish dry material is influenced, and the continuous casting industry is influenced.
CN108178641a provides a tundish dry material and a preparation method thereof, and the tundish dry material is obtained by magnesia powder, wustite powder, carbonaceous binder and additives, and has the advantages of low production cost, high sintering activity of the product, long service life and the like.
However, because the carbonaceous binder, especially the carbohydrate binder, is decomposed at a relatively low temperature, the problems such as paste molding and the like may occur in the preparation process, and the corrosion resistance and the service life of the intermediate temperature are affected, a new tundish dry material needs to be provided to improve the processing and the service performance.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a long-life continuous casting tundish dry material, which is prepared from 90-95 parts by weight of magnesia, 5-10 parts by weight of a binding agent, 5-10 parts by weight of a binding promoter and 1-3 parts by weight of an antioxidant.
Magnesia sand
In one embodiment, the magnesite of the present invention is fused magnesite and/or sintered magnesite. The grain diameter of the magnesia is 0.05-5 mm. The grain size of the magnesite is within 0.05-5 mm, and the specific grain size distribution is not particularly limited.
Binding agent
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 bonding agent of the present invention further comprises a silicon-based bonding agent comprising one or more of metasilicate, magnesium aluminum silicate, silicate.
More preferably, the weight ratio of the saccharide binder to the silicon binder is 1: (0.5-1.5).
Further preferably, the metasilicate of the present invention is selected from one or more of anhydrous metasilicate, pentahydrate metasilicate, nonahydrate metasilicate. Such as sodium metasilicate.
The carbohydrate binder is used as an environment-friendly binder, so that environmental pollution during the preparation and use of the tundish can be avoided, but the inventor finds that caramel is easy to form and even further carbonize during the low-temperature sintering molding in the preparation process of the carbohydrate binder, especially sucrose and the like, so that the problems of paste molding and the like are caused.
The inventors have unexpectedly found that by using a combination of a silicon-based binder and a saccharide-based binder, particularly a combination of hydrous metasilicate and sucrose as a binder, the problems of avoiding contamination, improving environmental protection, promoting the stability of molding and demolding, avoiding sticking and the like are also promoted.
This is probably because by using an aqueous metasilicate, on the one hand the metasilicate and sucrose co-act under the action of water to form a gel system, and on the other hand the metasilicate and gel system structure shrink as the water volatilizes and caramel or other carbides are formed, so that the metasilicate is covered around the caramel and other substances, avoiding the action with moulds, thus promoting the stability of moulding and demoulding.
Furthermore, the inventors have found that the stability of molding and demolding is more readily promoted with respect to the structure of the pentahydrate metasilicate, probably because more combinations promote the formation of a more homogeneous gel system and the coverage of metasilicate.
Binding promoters
In one embodiment, the binding promoter of the present invention is selected from one or more of clay, diatomaceous earth, kaolin.
Preferably, the kaolin according to the invention has a particle size of 100 to 300 μm. The particle size of the kaolin is 100-300 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 in a weight ratio of 1: (3-4).
The inventor finds that although the addition of the hydrous metasilicate is favorable for demolding and forming, the volatilization of more water also causes loose structure in the middle-temperature use process and easy corrosion of steel slag, and the inventor unexpectedly finds that the combination of the kaolin, especially the hard kaolin and the soft kaolin can promote the improvement of corrosion resistance, especially the long-term corrosion resistance and the service life.
The inventors found that this is probably because, on the one hand, the kaolin layer-like structure, in particular the porous, loose crystalline structure of the more soft kaolin, defines the path of water evaporation, reduces the number and size of pores, reduces apparent porosity, and on the other hand, the less amorphous, dense hard kaolin adsorbs around the soft kaolin, supports the structure of the soft kaolin, even because of its denser texture, enters the interior of the soft kaolin and metasilicate, further adjusts the dense structure of the surface layer of the tundish, avoiding penetration and further erosion of steel slag.
In addition, the inventors have found that it is necessary to control the amount of soft and hard kaolin, and when hard kaolin is high, it is difficult to define and guide the number and size of pores, so that the surface layer structure of the tundish is more evacuated, and the resistance is adversely affected.
Antioxidant
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 inventors found that more soft kaolin, although improving the corrosion resistance, also affects the increase of the bulk density during the middle temperature calcination because of its porous structure, and that it is difficult to form a highly dense tundish, affecting the pressure resistance and fracture resistance, whereas the inventors unexpectedly found that the use of nano antioxidants, especially nano aluminum powder, is advantageous in promoting further improvement of the corrosion resistance and the obtaining of a more dense structure.
This is probably because by using nano alumina, the surface property and small particle size of the nano alumina powder are utilized, and the nano alumina powder is favorable for entering the kaolin, especially the inside of porous soft kaolin, at this time, as the intermediate temperature is calcined and oxidized, the nano alumina powder is subjected to volume expansion to form alumina and the like, so that gaps of the kaolin can be partially filled, and the nano alumina powder can react with the silicon oxygen tetrahedron of the kaolin and the crystal structure of aluminum oxyhydrogen octahedral, so that the crystal structure of the soft kaolin is rearranged, the compactness of the kaolin is further promoted, and as the intermediate temperature is carried out, oxides such as magnesium in magnesia are further subjected to solid solution combination with a binding agent, an antioxidant and a binding promoter, and the volume density and the corrosion resistance are promoted.
In addition, the inventors 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 is easily affected, thereby adversely affecting the corrosion resistance.
The second aspect of the invention provides a method for preparing the long-life continuous casting tundish dry material, which comprises the following steps: and (3) blending, sintering and demolding the magnesia, the binding agent, the binding accelerator and the antioxidant to obtain the tundish dry material.
The inventor finds that by using the magnesia, the bonding agent, the bonding accelerator and the antioxidant provided by the invention to act together, the corrosion resistance and the processing performance can be improved, the service life of the tundish is prolonged, the phenomenon of carburetion and steel increment of molten steel caused by carbon residue of a carbohydrate bonding agent is avoided, the formed steel has smooth surface and no hole and the like, and the invention can be used for processing low-carbon steel and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses the combined action of the silicon binding agent and the saccharide binding agent, especially the combined action of the hydrous metasilicate and the sucrose as the binding agent, thereby avoiding pollution, improving the environmental protection, simultaneously promoting the stability of molding and demolding, avoiding the problems of sticking and the like.
(2) The inventors have found that by using kaolin, especially hard kaolin and soft kaolin, in combination, an increase in corrosion resistance, especially long term corrosion resistance, and an increase in service life can be promoted.
(3) The inventors found that by using nano antioxidants, in particular nano aluminum powder, it is advantageous to promote further improvement of the corrosion resistance and the obtaining of a denser structure.
(4) By using the combined action of the magnesia, the binding agent, the binding promoter and the antioxidant, the corrosion resistance and the processing performance can be improved, the service life of the tundish is prolonged, the phenomenon of carburetion and steel increment of molten steel caused by carbon residue of a carbohydrate binding agent and the like can be avoided, the formed steel has smooth surface and no hole and the like, and the invention can be used for processing low-carbon steel and the like.
Detailed Description
Examples
Example 1
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia and 8 parts by weight of a binding agent; the binding agent is sucrose.
The example provides a preparation method of the long-life continuous casting tundish dry material, which comprises the following steps: and (3) blending magnesia and a binding agent, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 2
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia and 8 parts by weight of a binding agent; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1.
the example provides a preparation method of the long-life continuous casting tundish dry material, which comprises the following steps: and (3) blending magnesia and a binding agent, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 3
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia, 8 parts by weight of a binding agent and 6 parts by weight of kaolin; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1, wherein the particle size of the kaolin is 100-300 mu m, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1:3.5.
the example 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 and kaolin, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 4
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia, 8 parts by weight of a binding agent, 6 parts by weight of kaolin and 2 parts by weight of an antioxidant; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1, wherein the particle size of the kaolin is 100-300 mu m, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: and 3.5, the antioxidant is nano aluminum powder.
The example 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, kaolin and an antioxidant, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 5
The example provides a long-life continuous casting tundish dry material, which is prepared from the following raw materials in parts by weight; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1.2, the grain diameter of the kaolin is 100-300 mu m, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: and 4, the antioxidant is nano aluminum powder.
The example 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, kaolin and an antioxidant, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 6
The example provides a long-life continuous casting tundish dry material, which is prepared from the following raw materials in parts by weight; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:0.5, wherein the grain diameter of the kaolin is 100-300 mu m, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: and 3, the antioxidant is nano aluminum powder.
The example 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, kaolin and an antioxidant, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 7
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia, 8 parts by weight of a binding agent and 6 parts by weight of kaolin; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1, wherein the particle size of the kaolin is 100-300 mu m, and the kaolin comprises soft kaolin.
The example 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 and kaolin, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Example 8
The example provides a long-life continuous casting tundish dry material, which is prepared from 92 parts by weight of magnesia, 8 parts by weight of a binding agent, 6 parts by weight of kaolin and 2 parts by weight of an antioxidant; the bonding agent is sucrose and sodium metasilicate nonahydrate, and the weight ratio is 1:1, wherein the particle size of the kaolin is 100-300 mu m, the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1: and 3.5, the antioxidant is submicron aluminum powder.
The example 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, kaolin and an antioxidant, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
Evaluation of Performance
1. Paste molding properties: in the process of sintering at 300 ℃ for 3h forming and demolding, whether the problem of pasting mold exists or not is observed, wherein the grade 1 is continuously 10 times of sintering forming pasting-free mold, the grade 2 is continuously 8-9 times of sintering forming pasting-free mold, the grade 3 is continuously 6-7 times of sintering forming pasting-free mold, the grade 4 is continuously sintering forming pasting-free mold for 5 times and more, and the results are shown in table 1.
2. Resistance to corrosion: the sample of the hollow cylinder obtained by sintering at 300 ℃ for 3 hours is subjected to a corrosion resistance test, wherein steel slag (about containing 6% of metal iron, 50% of calcium oxide, 8% of magnesium oxide and 6% of manganese oxide) is added into the sample, and after sintering for 3 hours, 6 hours and 9 hours at 1500 ℃, the steel slag corrosion depth at the bottom of the sample is tested, wherein the 1 grade is less than 3mm in depth, the 2 grade is less than or equal to 5mm in depth, more than 3mm, the 3 grade is less than 8mm in depth, more than 5mm, the 4 grade is less than or equal to 12mm in depth, more than 8mm, the 5 grade is less than or equal to 16mm in depth, more than 12mm, the 6 grade is less than or equal to 20mm in depth, more than 16mm and the 7 grade is more than 20mm in depth, and the results are shown in table 1.
3. Bulk density: 300 DEG CAfter 3h of sintering, the bulk density was measured according to GB T4513.6 after 3h of sintering at 1500℃where class 1 is a bulk density of greater than 2.6g/cm 3 Grade 2 is a bulk density of 2.6g/cm or less 3 Greater than 2.4g/cm 3 Grade 3 is a bulk density of 2.4g/cm or less 3 Greater than 2.2g/cm 3 Grade 4 is a bulk density of 2.2g/cm or less 3 The results are shown in Table 1.
Table 1 performance characterization test
The test result shows that the tundish dry material provided by the invention can be used for continuous casting of steel, has a long service life, and can not introduce impurities into the steel.
Claims (1)
1. The long-life continuous casting tundish dry material is characterized by comprising, by weight, 92-95 parts of magnesia, 8-9 parts of a binding agent, 6-8 parts of a binding promoter and 2-3 parts of an antioxidant; the antioxidant is a nano antioxidant; the nanometer oxidant is nanometer aluminum powder; the bonding agent is saccharide bonding agent and silicon bonding agent; the saccharide binding agent is sucrose; the silicon-based binding agent is metasilicate; the weight ratio of the saccharide bond to the silicon bond is 1: (0.5 to 1.5); the metasilicate is metasilicate nonahydrate; the binding promoter is kaolin; the particle size of the kaolin is 100-300 mu m; the kaolin comprises hard kaolin and soft kaolin, and the weight ratio is 1:3.5; the preparation method of the long-life continuous casting tundish dry material comprises the following steps: and (3) blending magnesia, a bonding agent, kaolin and an antioxidant, sintering at 300 ℃ for 3h, forming and demolding to obtain the tundish dry material.
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