CN108178641B - Tundish dry material and preparation method thereof - Google Patents
Tundish dry material and preparation method thereof Download PDFInfo
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- CN108178641B CN108178641B CN201810038472.4A CN201810038472A CN108178641B CN 108178641 B CN108178641 B CN 108178641B CN 201810038472 A CN201810038472 A CN 201810038472A CN 108178641 B CN108178641 B CN 108178641B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
A novel tundish dry material and a preparation method thereof belong to the technical field of refractory materials, and the tundish dry material comprises, by weight, 83-88% of sintered magnesia, 5-10% of wurtzite, 1-5% of alumina micropowder, 4-5% of carbonaceous binder and 2-3% of other additives. The preparation method comprises the following steps: (1) premixing magnesia powder, wustite powder, a carbonaceous binding agent and an additive in a sand mixer for 20-25 minutes, and uniformly mixing to obtain premixed powder; (2) and adding magnesia particles into the premixed powder, and further mixing for 15-20 minutes to obtain the tundish dry material. The tundish dry material and the preparation method thereof have the advantages of low production cost, high sintering activity of the product, long service life and good application prospect.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a tundish dry material and a preparation method thereof.
Background
The dry material of the tundish is a refractory material for a working lining of the tundish which is commonly applied. When the tundish dry material is used, the tundish dry material is eroded and washed by molten steel and molten slag, refractory raw material particles in the dry material fall off, and a dry material layer becomes thinner gradually until the tundish dry material layer cannot be used. The falling of the refractory raw materials in the dry material of the tundish not only influences the service life of the tundish and influences energy conservation and emission reduction, but also forms nonmetallic inclusions in steel if the fallen refractory materials cannot float upwards in time after entering molten steel, and seriously influences the product quality. Therefore, the service life of the refractory for the tundish dry material is very important in the continuous casting production process.
The existing dry tundish material is mainly made of a magnesia refractory material, namely, the refractory raw material takes magnesite of different grades as the main raw material. According to different combination modes, the method can be divided into carbon combination, inorganic salt combination, oxide micro powder combination and the like. Among them, carbon-bonded magnesium dry materials are widely used because of their good high temperature resistance and erosion resistance. However, in the baking and use process of the tundish, once the carbonaceous material as the binder phase falls off due to oxidation and the like, the magnesite fine powder in the matrix material is difficult to be effectively sintered at the use temperature, the bonding strength between particles in the decarburized layer is low, and the magnesite fine powder is easy to fall off under the scouring action of a molten pool, so that the service life of the dry material is influenced. Although the inorganic salt bonding and the oxide fine powder bonding can avoid the problem of low bonding strength of the decarburized layer due to carbon oxidation, the two bonding methods not only have the problem of high cost, but also cause deterioration of the erosion resistance of the dry material due to different introduction of impurity components.
Chinese patent (publication No. CN 101423417A) provides a low-carbon magnesia carbon brick containing metallic iron, which contains 1-8% of metallic iron, 83-94% of magnesia and 1-6% of carbon, is combined by 2.5-5% of carbon-containing bonding agent, and can be added with a small amount of antioxidant. Compared with the common magnesia carbon brick, the performance of the low-carbon magnesia carbon brick has the characteristics of less carburetion to molten steel and difficult pollution to ultra-low carbon steel. As magnesia is the main component, the magnesia carbon brick has good slag corrosion resistance. As carbon is one of the main components, the magnesia carbon brick has good slag penetration resistance and excellent thermal shock performance. The addition of the metallic iron improves the heat conductivity of the low-carbon magnesia carbon brick, generates a liquid phase at high temperature and reduces the internal stress. Thereby improving the thermal shock resistance of the low-carbon magnesia carbon brick.
Publication No. CN 103387396A) provides a magnesium iron carbon brick for a vanadium extraction converter and a preparation method thereof, which belong to the technical field of refractory materials, and the magnesium iron carbon brick for the vanadium extraction converter comprises 62-84% of fused magnesia, 10-18% of flaky graphite, 5-12% of iron powder, 1-3% of net-shaped fixed carbon and 0-5% of antioxidant by weight percentage; the preparation method comprises the following steps: (1) mixing the fused magnesia, the flaky graphite, the iron powder and the carbonaceous binder, adding or not adding an antioxidant, and uniformly mixing to obtain a mixed material; (2) pressing and forming the mixed material under the pressure of 200-250 MPa to prepare a green brick; (3) and (3) carrying out heat treatment on the green brick at the temperature of 150-250 ℃ for 12-32 hours to obtain the magnesia-iron-carbon brick for the vanadium extraction converter. The magnesium-iron-carbon brick for the vanadium extraction converter has good practical performance, simple preparation method and good application prospect.
Both patents disclose compositions of magnesite and iron elements, but both are added to the magnesia carbon refractory product in the form of metallic iron, and the compactness of the decarburized layer is improved by the volume expansion effect generated by the oxidation of the metallic iron. However, when the metal iron is added, the addition cost is high, and the compactness of the dry material after construction is easily affected by poor fluidity of the metal iron powder because the dry material of the tundish is not subjected to compression molding like a refractory product but vibration molding. In addition, the working time of the tundish is only 20-40 hours, and the metal iron powder is oxidized into FeO and then can further form a solid solution with MgO, so that the metal iron powder cannot form the solid solution in a short time and cannot be applied to the preparation of the tundish dry material.
Disclosure of Invention
Aiming at the problems existing in the using process of the conventional tundish dry material, the invention provides the tundish dry material and the preparation method thereof, and by virtue of novel component design, the bonding strength of a decarburized layer is improved, the scouring resistance of the decarburized layer is improved, and the service life of the tundish dry material is prolonged.
In order to realize the purpose of the invention, the following technical scheme is provided: the dry tundish material comprises, by weight, 83-88% of sintered magnesia, 1-5% of alumina micropowder, 4-5% of carbonaceous binder, and 2-3% of additive, and is characterized by further comprising 5-10% of wurtzite.
Preferably, the FeO content in the wustite is more than or equal to 95 percent, and the particle size is less than or equal to 200 meshes.
Preferably, the carbonaceous binder comprises at least one of phenolic resin and industrial sucrose, and the particle size is less than or equal to 100 meshes.
Preferably, the additive is aluminum powder, silicon powder and/or B4C, powder C, antioxidant with the weight purity more than or equal to 98 percent and the granularity less than or equal to 200 meshes.
To achieve the object of the present invention, there is provided a method for preparing a tundish dry material according to claim 1 or 2, characterized by comprising the steps of:
(1) premixing magnesia powder, siderite, alumina micropowder, a carbonaceous binder and an additive in a sand mixer for 20-25 minutes, and uniformly mixing to obtain premixed powder;
(2) and adding magnesia particles into the premixed powder, and further mixing for 15-20 minutes to obtain the tundish dry material.
Preferably, the volume density of the tundish dry material after vibration molding is 2.65-2.75g/cm3The apparent porosity is 21.4-22.3%, and the service life is 24-36 hours.
The magnesite is sintered magnesite, and the content of magnesium oxide in the magnesite is more than or equal to 90 percent.
Al in the above-mentioned fine alumina powder2O3The content is more than or equal to 98 percent, and the granularity is less than or equal to 325 meshes.
The FeO content in the square iron ore powder is more than or equal to 96 percent, and the granularity is less than or equal to 200 meshes.
The carbonaceous binder comprises at least one of phenolic resin and industrial sucrose, and the particle size is less than or equal to 100 meshes. The weight content of the fixed C in the phenolic resin is more than or equal to 40 percent.
It is well known that MgO and FeO can form an infinite solid solution. After FeO is added into the magnesium tundish dry material, under the high-temperature condition, as the FeO is dissolved into MgO in a solid way, the size of MgO grains is increased, the distance between MgO fine powder in a dry material matrix is reduced, and the growth of the grains and sintering densification are facilitated in the high-temperature use process; at the same time, Fe2+Substitution of Mg2+The formed MgO crystal defects are also beneficial to improving the sintering activity of the matrix part and promoting the sintering densification. With the sufficient sintering of the matrix part, the bonding strength among dry material particles is favorably improved, the anti-scouring performance of the tundish dry material is improved, and the service life of the dry material is prolonged. Meanwhile, with the reduction of the dosage of additives such as alumina micropowder and the like, the production cost is favorably reduced, the pollution of the additives to the components of the dry material is reduced, and the erosion resistance of the dry material is improved. Although the iron elements are Fe, FeO and Fe2O3、Fe3O4Etc. and FeO is stable phase in high temperature oxidizing atmosphere but in Fe2O3Or Fe3O4Form addition, Fe at high temperature2O3Or Fe3O4The addition of the iron-containing powder is accompanied by a significant volume shrinkage when converted into FeO, and the particle size of the added iron-containing powder is reduced, so that the contact degree between the generated FeO and MgO particles is deteriorated, and the solid solution rate of FeO into MgO is influenced, so that the addition effect is not as good as that when the tundish dry material is prepared.
The invention has the beneficial effects that:
according to the tundish dry material provided by the invention, after a carbonaceous binding agent is oxidized, the magnesiosidete is generated at the matrix part through the solid solution reaction of the periclase and the wustite under the high-temperature condition, and the effective sintering of the decarburized layer can be realized at the service temperature of the tundish by utilizing the volume expansion effect of the solid solution reaction and the sintering activity of the magnesium wustite generated in situ, so that the compactness, the sintering strength, the scouring resistance and the erosion resistance of the decarburized layer are improved, and the service life of the dry material can be obviously prolonged.
The dry material and the production method thereof have the advantages of simple process method, good performance of the dry material and good application prospect.
Detailed Description
The phenolic resin selected in the embodiment of the invention is commercial thermosetting liquid phenolic resin or industrial sucrose.
The sand mixer selected in the embodiment of the invention is an edge runner type sand mixer. (model S1410)
Example 1:
the adopted sintered magnesia accounts for 88 percent of the total weight of the dry material. Wherein, the MgO content in the magnesia with the thickness of 3-1mm is 90 percent, and the addition amount accounts for 35 percent of the total weight of the dry material; the MgO content in the 1-0mm magnesite is 90%, the adding amount accounts for 30% of the total weight of the dry material, the MgO content in the magnesite with the particle size less than or equal to 200 meshes is 92%, and the adding amount accounts for 23% of the total weight of the dry material;
al in the adopted alumina micro powder2O3The content is 98.5%, the granularity is less than or equal to 325 meshes, and the adding amount accounts for 5% of the total weight of the dry material
The adopted carbonaceous binder is phenolic resin, the weight content of the fixed C is 45%, and the addition amount accounts for 4% of the total weight of the dry material;
the adopted additive is aluminum powder, the weight purity is 98.5 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 3 percent of the total weight of the dry material;
premixing magnesia powder, square iron ore powder, alumina micro powder, phenolic resin and an additive in a sand mixer for 25 minutes, and uniformly mixing to obtain premixed powder;
and adding magnesia particles into the premixed powder, and further mixing for 20 minutes to obtain the tundish dry material.
The dry material produced by the method has the bulk density of 2.65 g/cm after being subjected to on-site vibration construction and baking at 200 DEG C3The apparent porosity is 22.3%, the normal-temperature compressive strength is 35.7MPa, and the service life is 24 hours.
Example 2:
the adopted sintered magnesia accounts for 85 percent of the total weight of the dry material. Wherein, the MgO content in the magnesia with the thickness of 3-1mm is 90 percent, and the addition amount accounts for 35 percent of the total weight of the dry material; the MgO content in the 1-0mm magnesite is 90%, the adding amount accounts for 30% of the total weight of the dry material, the MgO content in the magnesite with the particle size less than or equal to 200 meshes is 92%, and the adding amount accounts for 20% of the total weight of the dry material;
the weight purity of the adopted square iron ore powder is 95 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 5 percent of the total weight of the dry material;
al in the adopted alumina micro powder2O3The content is 98.5 percent, the granularity is less than or equal to 325 meshes, and the adding amount accounts for 4 percent of the total weight of the dry material
The adopted carbonaceous binder is phenolic resin, the weight content of the fixed C is 45%, and the addition amount accounts for 4% of the total weight of the dry material;
the adopted additive is aluminum powder, the weight purity is 99 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 2 percent of the total weight of the dry material;
premixing magnesia powder, square iron ore powder, alumina micro powder, phenolic resin and an additive in a sand mixer for 25 minutes, and uniformly mixing to obtain premixed powder;
and adding magnesia particles into the premixed powder, and further mixing for 20 minutes to obtain the tundish dry material.
The dry material produced by the method has the bulk density of 2.68 g/cm after being subjected to on-site vibration construction and baking at 200 DEG C3The apparent porosity is 22.1%, the normal-temperature compressive strength is 36.5MPa, and the service life is 28 hours.
Example 3:
the adopted sintered magnesia accounts for 83 percent of the total weight of the dry material. Wherein, the MgO content in the magnesia with the thickness of 3-1mm is 90 percent, and the addition amount accounts for 35 percent of the total weight of the dry material; the MgO content in the 1-0mm magnesite is 90%, the adding amount accounts for 30% of the total weight of the dry material, the MgO content in the magnesite with the particle size less than or equal to 200 meshes is 92%, and the adding amount accounts for 18% of the total weight of the dry material;
the weight purity of the adopted square iron ore powder is 95 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 8 percent of the total weight of the dry material;
al in the adopted alumina micro powder2O3The content is 98.5 percent, the granularity is less than or equal to 325 meshes, and the adding amount accounts for 2 percent of the total weight of the dry material
The adopted carbonaceous binder is phenolic resin, the weight content of the fixed C is 45%, and the addition amount accounts for 4% of the total weight of the dry material;
the adopted additive is aluminum powder, the weight purity is 98.5 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 2 percent of the total weight of the dry material;
premixing magnesia powder, square iron ore powder, alumina micro powder, phenolic resin and an additive in a sand mixer for 20-25 minutes, and uniformly mixing to obtain premixed powder;
and adding magnesia particles into the premixed powder, and further mixing for 15-20 minutes to obtain the tundish dry material.
The dry material produced by the method has the bulk density of 2.72 g/cm after being subjected to on-site vibration construction and baked at 200 DEG C3The apparent porosity was 21.8%, the room-temperature compressive strength was 36.1MPa, and the service life was 32 hours.
Example 4:
the adopted sintered magnesia accounts for 83 percent of the total weight of the dry material. Wherein, the MgO content in the magnesia with the thickness of 3-1mm is 90 percent, and the addition amount accounts for 35 percent of the total weight of the dry material; the MgO content in the 1-0mm magnesite is 90%, the adding amount accounts for 30% of the total weight of the dry material, the MgO content in the magnesite with the particle size less than or equal to 200 meshes is 92%, and the adding amount accounts for 18% of the total weight of the dry material;
the weight purity of the adopted square iron ore powder is 95 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 10 percent of the total weight of the dry material;
al in the adopted alumina micro powder2O3The content is 98.5 percent, the granularity is less than or equal to 325 meshes, and the adding amount accounts for 1 percent of the total weight of the dry material
The adopted carbonaceous binder is industrial sucrose, the weight content of the fixed C is 38 percent, and the adding amount accounts for 5 percent of the total weight of the dry material;
the adopted additive is aluminum powder, the weight purity is 98.5 percent, the granularity is less than or equal to 200 meshes, and the adding amount accounts for 2 percent of the total weight of the dry material;
premixing magnesite powder, square iron ore powder, alumina micro powder, industrial cane sugar and an additive in a sand mixer for 25 minutes, and uniformly mixing to obtain premixed powder;
and adding magnesia particles into the premixed powder, and further mixing for 20 minutes to obtain the tundish dry material.
The dry material produced by the method has the bulk density of 2.74 g/cm after being subjected to on-site vibration construction and baking at 200 DEG C3The apparent porosity is 22.4%, the normal-temperature compressive strength is 35.7MPa, and the service life is 36 hours.
Claims (5)
1. A dry tundish material comprises, by weight, 83-88% of sintered magnesia, 1-5% of alumina micropowder, 4-5% of carbonaceous binder, and 2-3% of additive, and is characterized by also comprising 5-10% of wustite, wherein the FeO content in the wustite is not less than 95%, and the particle size is not more than 200 meshes.
2. The tundish dry material of claim 1, wherein the carbonaceous binder comprises at least one of phenolic resin and industrial sucrose, and the particle size is less than or equal to 100 mesh.
3. A tundish dry material according to claim 1, wherein the additive is aluminium powder, silicon powder and/or B4C, powder C, antioxidant with the weight purity more than or equal to 98 percent and the granularity less than or equal to 200 meshes.
4. A method of making a tundish dry charge as claimed in any one of claims 1 to 3, comprising the steps of:
(1) premixing magnesite powder, siderite, alumina micropowder, carbonaceous binder and additive in a sand mixer for 20-25 minutes, and uniformly mixing to obtain premixed powder;
(2) adding magnesia particles into the premixed powder and further mixing for 15-20 minutes to obtain the tundish dry material.
5. The method as claimed in claim 4, wherein the bulk density of the tundish dry material after vibration molding is 2.65-2.75g/cm3The apparent porosity is 21.4-22.3%, and the service life is 24-36 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108526452B (en) * | 2018-04-19 | 2019-11-26 | 东北大学 | A kind of quick baking type tundish dry material and preparation method thereof |
| CN108840667A (en) * | 2018-07-30 | 2018-11-20 | 合肥铭佑高温技术有限公司 | A kind of preparation method of the high temperature resistant tundish dry material modified based on pyrophillite |
| CN109111234A (en) * | 2018-08-10 | 2019-01-01 | 河南弘盛再生资源利用有限公司 | Aluminium scrap ash reprocesses the formula and preparation method that homogeneous refractory raw material is made |
| CN109437938A (en) * | 2018-12-28 | 2019-03-08 | 江苏嘉耐高温材料有限公司 | A kind of liner in dundish castable |
| CN111116213A (en) * | 2019-02-21 | 2020-05-08 | 张家港市恒乐阳方高温材料有限公司 | Dry refractory material |
| CN110128152A (en) * | 2019-05-13 | 2019-08-16 | 天津炜润达新材料科技有限公司 | A kind of tundish dry material and preparation method thereof |
| CN113321492A (en) * | 2021-05-21 | 2021-08-31 | 泰州市旺鑫耐火材料有限公司 | Long-life tundish slag line dry material |
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