Melting-resistant fireproof material, manufacturing method and use thereof

Abstract

The present invention discloses a corrosion-resistant refractory material, a manufacturing method thereof and its use. In the corrosion-resistant refractory material, the phase of the refractory material includes corundum and one or more phases selected from CA6, C2M2A14, CM2A8 and ZrO2. The refractory material has a small amount of high-temperature liquid phase, a uniform pore structure, and excellent thermal shock stability, and can be widely used in steelmaking production lines and refractory linings of rotary kilns. It has good corrosion resistance and low thermal conductivity, and its performance is obviously superior to many existing refractory materials such as silica-mullite bricks and magnesia-alumina-spinel bricks.

Description

[Technical Field]

[0001] This application relates to the technical field of refractory materials, and in particular to erosion-resistant refractory materials, their manufacturing methods and their uses. [Background technology]

[0002] After molten iron is blown in a converter, due to the presence of more oxygen, the molten steel must undergo refining processes, mainly deoxidation, desulfurization, and removal of non-metallic inclusions, which usually require high temperatures and high alkalinity slag. The damage to refractories during the refining process is very serious, mainly due to the high temperature and high alkalinity slag.

[0003] Because high temperatures cause slag to corrode refractory materials quickly, the working linings used in ladle refining are generally made of relatively good refractory materials, with high raw material purity and good corrosion resistance. Currently used corundum-spinel castables, corundum-MgO-SiO2 castables, etc. are mainly made of corundum.

[0004] Refined slag is generally highly basic and has low viscosity, and is primarily used for desulfurization and to change the properties of inclusions. However, this also leads to the slag penetrating deep into the refractory material, which causes deterioration and dissolution of the refractory material. The large difference in the expansion coefficient and high-temperature performance of the metamorphic layer and the raw brick layer causes the refractory material to peel off and be damaged, which is a very fatal method of damage to the refractory material.

[0005] Unlike ceramics, refractories are generally subject to large temperature fluctuations and thermal stresses during use. Therefore, to prevent stress cracking and damage to the refractory during use, it is necessary to ensure a certain level of porosity in the refractory to buffer expansion stresses. For example, corundum-spinel castables have a porosity of 15-19%. These pores buffer expansion stresses and provide favorable conditions for the penetration of low-viscosity slag, which can cause penetration and spalling damage. Existing refractory preparation technologies and research concepts require a certain level of porosity to avoid stress damage and ensure thermal shock stability.

[0006] Therefore, the refractory materials used in ladles must satisfy three requirements: corrosion resistance, penetration resistance, and thermal shock stability. However, the thermal shock stability, penetration resistance, and corrosion resistance are mutually contradictory.

[0007] Magnesia-carbon bricks and alumina-magnesia-carbon bricks are currently the primary type of ladle lining material used in industrial applications. They are based on the idea of ​​adding graphite to a base of corrosion-resistant materials such as magnesia and corundum. Graphite's low wettability prevents slag and molten steel from penetrating the refractory. Its high thermal conductivity reduces temperature gradients within the refractory, alleviating thermal stress caused by sudden temperature changes and improving the refractory's thermal shock resistance. However, graphite-based materials present problems during use, particularly when smelting ultra-low carbon steel, due to the addition of carbon to the steel. Furthermore, graphite oxidation, which corresponds to increased porosity, can accelerate damage to such materials. Carbon-free refining ladle refractories are an important development direction.

[0008] Corundum-spinel or corundum-MgO-SiO2 castables are carbon-free refractory materials currently used in industry. The aggregates are plate-like corundum and spinel particles, and the fine powders are plate-like corundum, spinel, activated alumina fine powder, pure aluminate cement, etc. The raw materials for this type of castable are high-purity and highly corrosion-resistant, but the refractory materials used in the construction suffer from a trade-off between thermal shock stability, penetration resistance, and erosion resistance.

[0009] For carbon-free refractories, improved thermal shock stability is typically achieved by maintaining a certain porosity, but the presence of pores leads to reduced permeation resistance. Corrosion resistance is achieved by using highly purified raw materials with high corrosion resistance, but this leads to difficulties in sintering and the challenge of how to solve the permeation resistance problem. Permeation resistance is primarily improved by improving the sinterability and densification of the refractory. In addition to adjusting the particle size distribution, densification is achieved through the sintering process. Sintering is usually achieved through the liquid phase.

[0010] Because refractories are composed of aggregates of large particles and fine powders, large interparticle densification forces are required. Furthermore, the surface tension and dissolution driving forces of the liquid phase are very limited. Therefore, while liquid phase sintering can alter local morphology, it cannot alter the overall structure. Furthermore, it cannot effectively prevent slag penetration unless a large amount of liquid phase is present. This is impossible under the high-temperature, harsh conditions of steel refining. Furthermore, the presence of a large amount of liquid phase significantly reduces the thermal shock stability of the material, leaving the tradeoff between thermal shock stability, penetration resistance, and erosion resistance unresolved.

[0011] The structural formula of calcium hexaaluminate is CaO 6Al2O3 (abbreviated as CA6), its melting point is 1875°C, and its theoretical density is 3.79g / cm 3 The characteristics of this material are as follows: (1) It has good stability under low oxygen partial pressures, (2) calcium hexaaluminate has a lamellar stacking structure, and its crystal growth is anisotropic, with a slow growth rate along the C axis, making it difficult to sinter, and (3) when CA6 reacts with slag, it produces CA2 (abbreviation for CaO·2Al2O3) and CA (abbreviation for CaO·Al2O3), etc. At steelmaking temperatures, CA2 becomes solid and CA becomes liquid, and this solid-liquid mixed phase blocks pores and inhibits the penetration of slag.

[0012] The ability to inhibit slag penetration is very suitable for refractories that come into contact with molten materials, but the layered structure and anisotropic growth of the material reduce sinterability and make densification difficult, so the volume density is less than 3.0 g / cm 3 and raw materials with a volume density of 2.90 g / cm3 It is also difficult to prepare calcium hexaaluminate refractories exceeding this limit. Without high-density CA6 raw materials, it is impossible to produce high-density CA6 refractories.

[0013] Currently, additives such as SiO2 and TiO2 are often used to densify calcium hexaaluminate raw materials, but at high temperatures, a liquid phase appears, promoting densification and sintering. For example, Chen Zhaoyou and Chai Junlan, in "Calcium Hexaaluminate Materials and Their Application to Aluminum Industrial Furnaces" (Non-Patent Document 1), describe the physical and chemical properties of Bonite (a trade name for calcium hexaaluminate) and note that its chemical composition contains 0.9% SiO2. Furthermore, "Method for Preparing Dense Calcium Hexaaluminate Refractory Clinker" (Patent Document 1) and "Dense Calcium Hexaaluminate Refractory Clinker and Method for Preparing the Same" (Patent Document 2) use TiO2 and MnO as sintering agents, respectively. However, these methods do not achieve densification by controlling the atomic stacking within the mirror layer; instead, they only utilize a liquid phase to reduce the distance between particles, which limits the densification. Furthermore, in all methods of adding sintering aids to increase density, the high-temperature performance of the material is sacrificed, resulting in a significant decrease (although the amount added is less than 1%, it generates several times more liquid phase at high temperatures).

[0014] Refractories made from calcium hexaaluminate with added sintering aids have problems such as high apparent porosity (apparent porosity of the material is up to 35%) and poor corrosion resistance, in addition to defects inherent to the raw material. When the porosity is high and a large amount of sintering aid is added, the damage rate of calcium hexaaluminate refractories becomes very fast.

[0015] CaO·2MgO·8Al2O3 and 2CaO·2MgO·14Al2O3 are both based on the CA6 structural unit and C-axis stacking of MgO·Al2O3, and their properties are similar to those of CA6. For ease of explanation, we will refer to only CA6 below, and collectively refer to CaO·2MgO·8Al2O3 and 2CaO·2MgO·14Al2O3 as CMA. Furthermore, CA6 and CMA are collectively referred to as calcium hexaaluminate phases. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Chinese Patent Application Publication No. CN110171980A [Patent Document 2] Chinese Patent Application Publication No. CN105585314A [Non-patent literature]

[0017] [Non-Patent Document 1] Chen Zhaoyou et al., Calcium hexaaluminate material and its application to aluminum industrial furnaces [J]. Refractory Materials, 2011, 45(2): 122~125. Summary of the Invention [Problem to be solved by the invention]

[0018] Therefore, based on the advantages of calcium hexaaluminate's chemical composition, how can the density and structural uniformity of the material be significantly improved, the penetration of molten steel and slag reduced, the altered and damaged layers reduced, and the service life extended? How can the purity of calcium aluminate material be increased, its resistance to slag erosion improved, and its service life extended? These are of great importance for the refining of refractory materials for ladle linings and vessels such as aluminum refractory materials.

[0019] Based on the above analysis, the problems and deficiencies of the prior art are as follows: (1) To balance thermal shock stability and slag penetration resistance, refractories must maintain high porosity. This allows slag to penetrate deeply into the refractory, resulting in a thick metamorphic layer and subsequent erosion and spalling damage. (2) To ensure corrosion resistance, most raw materials are highly pure, but sintering is difficult. To achieve sintering and densification of the green body, sintering aids must be added to lower the melting point and increase the liquid phase, resulting in reduced slag erosion resistance. (3) The addition of sintering aids promotes sintering and densification, but only changes the local microstructure; the overall structure remains sparse. While the material is densified, the structural uniformity is poor. (4) Currently, there is no large-scale production of dense CA6 refractory raw materials. Although a small amount of dense CA6 raw materials is produced, the raw materials contain sintering aids such as SiO2. (5) The presence of a large amount of sintering aid liquid phase significantly reduces the thermal shock stability of the material. (6) The contradiction between thermal shock stability, penetration resistance, and corrosion resistance has not yet been resolved.

[0020] The difficulties in resolving the above problems and deficiencies are as follows: (1) In conventional refractory development, the pore distribution is highly uneven, whether in castables or firebricks. To mitigate stress damage caused by temperature changes, a large amount of porosity is required to counteract the uneven pore distribution, making slag penetration inevitable and difficult to control. (2) The only way to improve slag erosion resistance is to increase the purity of the raw materials, but high-purity raw materials are difficult to sinter through particle diffusion alone, and strength cannot be guaranteed. (3) High-purity refractory systems can achieve liquid-phase sintering and achieve strength only by adding sintering aids, but the appearance of a low-melting liquid phase reduces corrosion resistance. (4) CA6 materials are difficult to sinter due to their structural characteristics. While densification can be achieved by adding sintering aids, this results in reduced high-temperature performance, significantly reduced slag erosion resistance, and reduced thermal shock stability. (5) In conventional refractory development, it is difficult to achieve high density by utilizing close-packed particle stacking and the surface tension of the liquid phase.

[0021] The significance of solving these problems and shortcomings is as follows: Using high-purity, corrosion-resistant raw materials as a base, high-purity, corrosion-resistant refractories can be produced without the addition of sintering aids, the formation of a low-melting-point liquid phase, or relying on liquid phase sintering, thereby maximizing the corrosion-resistant advantages of high-purity raw materials; constructing refractories with a uniform structure not only resolves the structural stress of the entire refractory, but also solves the problem of slag penetration resistance, achieving both penetration resistance and thermal shock resistance; this not only fully utilizes the advantages of high-purity raw materials with excellent corrosion resistance, but also achieves both thermal shock stability and slag penetration resistance, solving the problem of rapid damage to refractories in ladle working linings under harsh refining conditions, bringing significant economic and social benefits. [Means for solving the problem]

[0022] In order to solve the above problems, the present invention provides a refractory material having high resistance to corrosion, a method for producing the same, and use of the same.

[0023] The highly corrosion-resistant refractory material of the present invention does not require the addition of sintering aids during the manufacturing process, and can be manufactured using a hot-press sintering process to produce refractory products with high purity, good corrosion resistance, good slag penetration resistance, and high thermal shock stability.

[0024] The specific technical solutions of the present invention are as follows: 1. A corrosion-resistant refractory material, wherein the phases of the refractory material include corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO2. 2. The total mass percentage of corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO2 in the phases of the refractory material is 90% or more; Preferably, the corundum phase is 26.5 to 89.5%, preferably 32 to 89.5%, more preferably 32.0 to 88.0%, the total amount of CA6+C2M2A14+CM2A8 is 5.25 to 66.5%, preferably 5.25 to 62.0%, and more preferably 6.0 to 62.0%, Item 2. The refractory material according to item 1, wherein the ZrO2 phase is 0 to 35%, preferably 0 to 30%. 3. The refractory material according to item 1 or 2, wherein the content of impurity components that promote sintering is 1.5% or less, preferably 1.0% or less, by mass percentage in the refractory material. 4. The refractory material according to any one of items 1 to 3, wherein the chemical composition of the refractory material includes Al2O3, CaO, MgO, and ZrO2, and the Al2O3 is 59.5 to 98.99%, preferably 64.57 to 98.99%, the CaO is 0.30 to 5.58%, preferably 0.35 to 5.58%, and more preferably 0.30 to 5.20% or 0.35 to 5.20%, the MgO is 0 to 5.58%, and the ZrO2 is 0 to 35%, as mass percentages in the refractory material. 5. The volume density of the refractory material is 2.90 to 3.65 g / cm 3 and preferably 2.95 to 3.45 g / cm 3 and more preferably 2.95 to 3.30 g / cm 3 5. The fire-resistant material according to any one of items 1 to 4, 6. The fire-resistant material is aggregate and fine powder to obtain a mixed material, and hot-press sintering the mixed material to obtain the refractory material. Item 6. The fire-resistant material according to any one of items 1 to 5, which is produced by a method comprising: 7. The above aggregate and the fine powder in a mass ratio of 30-65:35-70. 8. The above aggregate But corundum aggregate Mixed with aggregate and preferably aggregate As a mass percentage of the corundum aggregate is 65 to 100%, and aggregate is 0 to 35%, Preferably, the mixing aggregate is CA6 aggregate , C2M2A14 aggregate , and CM2A8 aggregate and one or more selected from Preferably, the corundum aggregate is tabular corundum aggregate , sintered corundum aggregate , white corundum aggregate , dense corundum aggregate , and sub-white corundum aggregate one or more selected from Item 6 or 7. The fire-resistant material according to item 6 or 7. 9. The fine powder contains Al2O3-CaO-MgO-based fine powder and ZrO2-containing fine powder, and preferably, the mass percentage of the Al2O3-CaO-MgO-based fine powder is 50% to 100%, and the mass percentage of the ZrO2-containing fine powder is 0 to 50% in the fine powder; Preferably, the Al2O3-CaO-MgO-based fine powder comprises an Al2O3-containing fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8, and MgO-CaO-based fine powders; Preferably, the MgO-CaO-based fine powder is an MgO-containing fine powder and / or a CaO-containing fine powder, Preferably, the Al2O3-containing fine powder is one or more fine powders selected from activated α-Al2O3 fine powder, γ-Al2O3 fine powder, ρ-Al2O3 fine powder, aluminum hydroxide fine powder, industrial alumina fine powder, white corundum fine powder, sintered corundum fine powder, and plate-like corundum fine powder; Preferably, the MgO-containing fine powder is one or more fine powders selected from magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, high-purity magnesia, and electrofused magnesia; Preferably, the CaO-containing fine powder is one or more selected from quicklime, limestone, calcium hydroxide, CaO·Al2O3, CaO·2Al2O3, 12CaO·7Al2O3, CA6, C2M2A14, and CM2A8; Preferably, the ZrO2-containing fine powder is one or more selected from the group consisting of a monoclinic zirconia fine powder, a tetragonal zirconia fine powder, a desiliconized zirconia fine powder, and an electrofused zirconia fine powder. 10. The particle size of the fine powder is 0.088 mm or less, and preferably, aggregate The particle size is 0.088 Larger than mm 10mm below and preferably 0.088 Larger than mm 8mm below Item 10. The fire-resistant material according to any one of items 6 to 9, wherein 11. The refractory material according to any one of items 6 to 10, wherein the hot press sintering is performed by placing the mixed material in a mold of a high-temperature device and hot press sintering, or by molding the mixed material at room temperature and then placing it in a mold of a high-temperature device and hot press sintering, or by molding the mixed material at room temperature, pre-sintering it at a low temperature, and then hot press sintering it. 12. The refractory material according to item 11, wherein the temperature of the hot press sintering is 1550 to 1800°C, and preferably the hot press strength is 0.5 to 30 MPa. 13. aggregate and fine powder to obtain a mixed material, and hot-press sintering the mixed material to obtain a refractory material. A method for producing the refractory material, comprising: 14. The aforementioned aggregate and the fine powder in a mass ratio of 30-65:35-70. 15, the above aggregate But corundum aggregate Mixed with aggregate and preferably aggregate As a mass percentage of the corundum aggregate is 65 to 100%, and aggregate is 0 to 35%, Preferably, the mixing aggregate is CA6 aggregate , C2M2A14 aggregate , and CM2A8 aggregate and one or more selected from Preferably, the corundum aggregateItem 13 or 14, wherein the corundum is one or more selected from plate-like corundum, sintered corundum, white corundum, dense corundum, and sub-white corundum. 16. The fine powder comprises an Al2O3-CaO-MgO-based fine powder and a ZrO2-containing fine powder, and preferably, the Al2O3-CaO-MgO-based fine powder accounts for 50% to 100% by mass, and the ZrO2-containing fine powder accounts for 0% to 50% by mass, Preferably, the Al2O3-CaO-MgO-based fine powder comprises an Al2O3-containing fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8, and MgO-CaO-based fine powders; Preferably, the MgO-CaO-based fine powder is an MgO-containing fine powder and / or a CaO-containing fine powder, Preferably, the Al2O3-containing fine powder is one or more fine powders selected from activated α-Al2O3 fine powder, γ-Al2O3 fine powder, ρ-Al2O3 fine powder, aluminum hydroxide fine powder, industrial alumina fine powder, white corundum fine powder, sintered corundum fine powder, and plate-like corundum fine powder; Preferably, the MgO-containing fine powder is one or more fine powders selected from magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, sintered magnesia, and fused magnesia; Preferably, the CaO-containing fine powder is one or more selected from quicklime, limestone, calcium hydroxide, CaO·Al2O3, CaO·2Al2O3, 12CaO·7Al2O3, CA6, C2M2A14, and CM2A8; Preferably, the ZrO2-containing fine powder is one or more selected from the group consisting of a monoclinic zirconia fine powder, a tetragonal zirconia fine powder, a desiliconized zirconia fine powder, and an electrofused zirconia fine powder. 17. The particle size of the fine powder is 0.088 mm or less, and preferably, aggregate The particle size is 0.088 Larger than mm 10mm below and preferably 0.088 Larger than mm 8mm below Item 17. The method according to any one of Items 13 to 16, wherein 18. The manufacturing method according to any one of items 13 to 17, wherein the hot press sintering is carried out by placing the mixed material in a mold of a high-temperature device and hot press sintering, or by molding the mixed material at room temperature and then placing it in a mold of a high-temperature device and hot press sintering, or by molding the mixed material at room temperature, pre-sintering it at a low temperature, and then placing it in a mold of a high-temperature device and hot press sintering. 19. The manufacturing method according to item 18, wherein the temperature of the hot press sintering is 1550 to 1800°C, and preferably the hot press strength is 0.5 to 30 MPa. 20. A working lining for a ladle for molten steel refining, comprising the refractory material according to any one of items 1 to 12, or the refractory material manufactured by the manufacturing method according to any one of items 13 to 19. 21. A work lining for smelting molten aluminum and transporting a ladle, comprising the refractory material according to any one of items 1 to 12, or the refractory material manufactured by the manufacturing method according to any one of items 13 to 19. 22. A refractory lining for an industrial furnace, comprising the refractory material according to any one of items 1 to 12, or the refractory material manufactured by the manufacturing method according to any one of items 13 to 19. [Effects of the Invention]

[0025] (1) The refractory material provided by the present invention does not use any sintering-promoting components during the manufacturing process, and is sintered not in a liquid phase but at high temperature and pressure to promote granular rearrangement and particle diffusion. As a result, the refractory material provided by the present invention has good high-temperature performance, a uniform microstructure, and good thermal shock stability. (2) The refractory material provided by the present invention has a total content of sintering-promoting components, such as SiO2, TiO2, Fe2O3, and R2O (a collective term for K2O and Na2O), introduced from the raw materials of 1.5% or less. The purity of the chemical composition of the material is high, which is higher than that of refractories containing calcium hexaaluminate phases produced using existing technology. This allows the performance advantages of high-purity raw materials to be fully utilized, and the refractory material has excellent slag erosion resistance. (3) The phases of the refractory material provided by the present invention contain corundum and one or more of CA6, C2M2A14, CM2A8, and ZrO2, and the total phase content, as a mass percentage of the phases of the refractory material, is 90% or more. The phase purity is high, and when the CA6-based phase components react with slag, they produce solid-liquid components containing CA2, CA, etc., which block pores and improve the slag erosion resistance of the material. (4) The volume density of the fireproof material provided by the present invention is 2.90 to 3.65 g / cm 3 This is much higher than the volume density of refractory materials containing calcium hexaaluminate-based phases produced by conventional techniques. As long as the high purity of the material is maintained, the material of the present invention, which has a high volume density, exhibits significantly improved resistance to mechanical wear by molten steel and slag, improved resistance to slag penetration, and significantly extended service life. (5) The refractory material provided by the present invention has a uniform structure and is free from large pores concentrated in one area, which prevents localized progressive damage. It corrodes slowly and evenly during use, and is free from peeling and delamination or major damage, thereby significantly extending its service life. (6) The manufacturing method provided by the present invention uses simple raw materials and can satisfactorily sinter a high-purity refractory material containing a calcium hexaaluminate phase by a hot-press sintering process without using any sintering-promoting components, and the method is scientific and rational. (7) The corrosion-resistant refractory material provided by the present invention can be widely used in steelmaking production lines, such as the working lining of the refining ladle outside the furnace. With good corrosion resistance, it can significantly reduce the damage to the refractory material and the impact on the molten steel in the smelting process of high-grade special steel, improve the overall quality of high-grade special steel in China's metallurgical industry, increase the operating cycle of the equipment, and improve the economy, thereby bringing significant social benefits. (8) The corrosion-resistant refractory material of the present invention can be widely used in the refractory lining of rotary kilns, such as the transition zone of a cement rotary kiln. It has good corrosion resistance and low thermal conductivity, and its performance is significantly superior to many existing refractory materials such as silica-mullite bricks and magnesia-alumina spinel bricks, thereby extending the operating cycle of the equipment, reducing heat loss, and improving economic benefits. (9) The corrosion-resistant refractory material of the present invention has very low sensitivity to atmospheric conditions and can be widely used in the masonry of industrial kilns, such as petrochemical cracking furnaces, which are subject to high temperatures, reducing atmospheres, and alkaline atmosphere erosion. Its excellent stability, low thermal conductivity, and corrosion resistance are significantly superior to many existing refractory materials, such as corundum bricks, and can extend the operating cycle of equipment, reduce heat loss, and improve economic benefits. [Brief explanation of the drawings]

[0026] [Figure 1A] FIG. 1A is a schematic diagram showing the effect of the castable obtained in Comparative Example 1 after it has been eroded by dynamic rotating slag. [Figure 1B] FIG. 1B is a schematic diagram showing the effect of the refractory material described in Example 1 after being eroded by a dynamic rotating slug. [Figure 2A] FIG. 2A is a schematic diagram of the static crucible method for refining molten steel in Experimental Example 2, in which 1 is slag, 2 is an alumina crucible, 3 is steel, 4 is aluminum, and 5 is a refractory crucible. [Figure 2B] 2B is an effect diagram showing the erosion state over time of the castable obtained in Comparative Example 1 after molten steel refining by the static crucible method and the refractory material described in Example 1. a, b, and c are the profile structures of the castable obtained in Comparative Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively, and d, e, and f are the profile structures of the refractory material obtained in Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively. [Figure 2C] FIG. 2C is a schematic diagram showing the comparative effect of the microstructure of the castable obtained in Comparative Example 1 and the refractory material described in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will now be described in detail in conjunction with the embodiments illustrated in the drawings, where like numerals represent like features throughout the drawings. While specific embodiments of the present invention are illustrated in the drawings, it should be understood that the present invention may be embodied in various forms and is not limited to the embodiments set forth herein. Rather, these embodiments are provided to provide a more complete understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.

[0028] It should be noted that specific terms are used in the present specification and claims to refer to specific components. Those skilled in the art will understand that different terms may be used to refer to the same component. In the present specification and claims, differences in nouns are not used to distinguish between components, but rather functional differences in the components are used as the basis for distinction. For example, the terms "comprise" or "include" used throughout the specification and claims are open terms and should be interpreted as "including but not limited to." The following descriptions in this specification are preferred embodiments for carrying out the present invention, but these descriptions are intended to illustrate the general principles of the present specification and do not limit the scope of the present invention. The scope of protection of the present invention should be determined by the appended claims.

[0029] The present application provides a corrosion-resistant refractory material, the phases of which include corundum and one or more of CA6, C2M2A14, CM2A8, and ZrO2.

[0030] The phases of the refractory material are determined by XRD. For example, the material to be measured is polished to less than 325 mesh and then scanned by an X-ray diffractometer. The diffraction data is analyzed and matched with a standard PDF (Powder Diffraction File) card to obtain the relevant phases. By fitting the diffraction data, the contents of the relevant phases are obtained.

[0031] The ZrO2 phase is fO2 and ZrO2 coexist and are difficult to separate, and their crystal shapes are similar. (1)H f The O2 phase is ZrO2. (2) Due to differences in temperature, process, etc., and the uneven distribution of elements (it is impossible to achieve complete uniformity), the final product may contain ZrO2-CaO solid solution, ZrO2-MgO solid solution, CaO·ZrO2, MgO·ZrO2, and other phases. When ZrO2-CaO solid solution, ZrO2-MgO solid solution, CaO·ZrO2, MgO·ZrO2, and other phases appear, first combine the XRF results to correct the ZrO2 content, then convert the ZrO2 content to zirconia phase, and convert the CaO and MgO dissolved or bonded in the form of CaO·ZrO2, MgO·ZrO2, etc. to CA6 and CMA (convert the CaO and MgO contents to CA6 and MA, and then convert them to CA6, CMA, etc. depending on the temperature or CaO-MgO-Al2O3 system components, etc.), and then normalize all these phases to 100% to calculate the percentage content of each phase.

[0032] Regarding the content of ZrO2 in the chemical composition, f Since O2 and ZrO2 coexist and are difficult to separate, the XRF in this patent calculates the HfO2 content as part of the ZrO2 content.

[0033] In a preferred specific embodiment of the present invention, the total mass percentage of the phases of the refractory material is 90% or more of corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO2; Preferably, the corundum phase is 26.5 to 89.5%, preferably 32 to 89.5%, more preferably 32.0 to 88.0%, the total amount of the CA6+C2M2A14+CM2A8 phase is 5.25 to 66.5%, preferably 5.25 to 62.0%, and more preferably 6.0 to 62.0%, The ZrO2 phase is 0 to 35%, preferably 0 to 30%.

[0034] For example, the total amount of the phases as a mass percentage of the refractory material phase may be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, etc. The corundum phase may be 26.5%, 32%, 34.75%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 89.5%, etc. The total amount of CA6+C2M2A14+CM2A8 phases may be 5.25%, 6%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 66.5%, etc. The ZrO2 phase may be 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc.

[0035] Here, the total amount of CA6+C2M2A14+CM2A8 phase refers to the content of CA6 when only CA6 is present in the phase, and refers to the content of C2M2A14 or CM2A8 phase when only C2M2A14 or CM2A8 phase is present. When CA6 and C2M2A14 are present in a phase, it refers to the total content of both. When C2M2A14 and CM2A8 are present in a phase, it refers to the total content of both phases. When CA6 and CM2A8 are present in a phase, it refers to the total content of both phases. When CA6, C2M2A14, and CM2A8 phases are present in the phase, it refers to the total content of the three phases.

[0036] In a preferred specific embodiment of the present invention, the content of impurity components that promote sintering is 1.5% or less, preferably 1.0% or less, by mass percentage in the refractory material.

[0037] For example, the content of the sintering-promoting impurity components, as a mass percentage of the refractory material, may be 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0, or any range therebetween.

[0038] The impurity components that promote sintering are SiO2, TiO2, Fe2O3, and R2O, where R2O refers to alkali metal oxides, and the impurity components that promote sintering refer to chemical compositions.

[0039] In a preferred specific embodiment of the present invention, the chemical composition of the refractory material includes Al2O3, CaO, MgO, and ZrO2, and the Al2O3 is contained in the refractory material in a mass percentage of 59.5 to 98.99%, preferably 64.57 to 98.99%, the CaO in a mass percentage of 0.30 to 5.58%, preferably 0.35 to 5.58%, more preferably 0.30 to 5.20% or 0.35 to 5.20%, the MgO in a mass percentage of 0 to 5.58%, and the ZrO2 in a mass percentage of 0 to 35%.

[0040] For example, the Al2O3 may be present as a mass percentage of the refractory material in an amount of 59.5%, 61.45%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98.5%, 98.99%, or any range therebetween; The CaO may be 0.30%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.58%, or any range therebetween; the MgO may be 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.58%, or any range therebetween; The ZrO2 may be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or any range therebetween.

[0041] The chemical composition of the refractory material is determined by fluorescence analysis, i.e., XRF, in accordance with GB / T21114-2007.

[0042] In a preferred specific embodiment of the present invention, the volume density of the refractory material is 2.90 to 3.65 g / cm 3 and preferably 2.95 to 3.35 g / cm 3and more preferably 2.95 to 3.30 g / cm 3 is.

[0043] For example, the volume density of the refractory material is 2.90 g / cm 3 , 2.91g / cm 3 , 2.92g / cm 3 , 2.93g / cm 3 , 2.94g / cm 3 , 2.95g / cm 3 , 2.96g / cm 3 , 2.97g / cm 3 , 2.98g / cm 3 , 2.99g / cm 3 , 3.00g / cm 3 , 3.05g / cm 3 , 3.10g / cm 3 , 3.15g / cm 3 , 3.20g / cm 3 , 3.25g / cm 3 , 3.30g / cm 3 , 3.35g / cm 3 , 3.40g / cm 3 , 3.45g / cm 3 , 3.50g / cm 3 , 3.55g / cm 3 , 3.60g / cm 3 , 3.65g / cm 3 , or any range therebetween.

[0044] The volume density of the refractory material is measured in accordance with GB / T2997-2000.

[0045] In a preferred specific embodiment of the present invention, the refractory material comprises: aggregate and fine powder to obtain a mixed material, and hot-press sintering the mixed material to obtain a refractory material. It is produced by a method comprising:

[0046] The aforementioned aggregateThis refers to the portion that cannot be sieved through a 180-mesh square-hole sieve (Xinxiang Zhongtuo Machinery Equipment Co., Ltd.), i.e., the portion above the 180-mesh square-hole sieve. aggregate The particle size is 180 mesh ~ 10 mm, that is, the particle size is 0.088 Larger than mm 10mm or less, preferably 0.088 Larger than mm 8mm or less. For example, aggregate The particle size of 、0 The thickness may be 0.090mm, 0.095mm, 0.10mm, 0.15mm, 0.20mm, 0.25mm, 0.30mm, 0.35mm, 0.40mm, 0.45mm, 0.50mm, 0.55mm, 0.60mm, 0.65mm, 0.70mm, 0.75mm, 0.80mm, 0.85mm, 0.90mm, 0.95mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, or any range therebetween.

[0047] The fine powder refers to the part that has passed through a 180 mesh square hole sieve, that is, the part that is below the 180 mesh square hole sieve, and its particle size is 180 mesh or less, that is, the particle size is 0.088 mm or less.

[0048] The hot press sintering refers to a method of achieving sintering and preparation of materials under the combined action of applied pressure and temperature.

[0049] In a preferred specific embodiment of the present invention, aggregate and the fine powder have a mass ratio of 30-65:35-70.

[0050] For example, aggregate and the fine powder by mass ratio (i.e., aggregateThe mass ratio of the powder to the fine powder (mass ratio of the powder to the fine powder) may be 30 / 70, 31 / 69, 32 / 68, 33 / 67, 34 / 66, 35 / 65, 36 / 64, 37 / 63, 38 / 62, 39 / 61, 40 / 60, 41 / 59, 42 / 58, 43 / 57, 44 / 56, 45 / 55, 46 / 54, 47 / 53, 48 / 52, 49 / 51, 50 / 50, 51 / 49, 52 / 48, 53 / 47, 54 / 46, 55 / 45, 56 / 44, 57 / 43, 58 / 42, 59 / 41, 60 / 40, 61 / 39, 62 / 38, 63 / 37, 64 / 36, 65 / 35, or any range therebetween.

[0051] In a preferred specific embodiment of the present invention, aggregate But corundum aggregate Mixed with aggregate and preferably aggregate As a mass percentage of the corundum aggregate is 65 to 100%, and aggregate is 0 to 35%, Preferably, the mixing aggregate is CA6 aggregate , C2M2A14 aggregate , and CM2A8 aggregate and one or more selected from Preferably, the corundum aggregate is tabular corundum aggregate , sintered corundum aggregate , white corundum aggregate , dense corundum aggregate , and sub-white corundum aggregate One or more selected from:

[0052] aggregate As a mass percentage of the corundum aggregate may be, for example, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any range therebetween; The above-mentioned mixing aggregate may be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or any range therebetween.

[0053] C2M2A14 aggregate is 2CaO·2MgO·14Al2O3 aggregate Refers to CM2A8 aggregate CaO·2MgO·8Al2O3 aggregate Refers to...

[0054] The plate-like corundum aggregate It has a coarse and well-developed α-Al2O3 crystal structure, an Al2O3 content of more than 97.0%, a plate-like crystal structure, small pores and many closed pores.

[0055] The sintered corundum aggregate It refers to a refractory clinker made by crushing alumina into pellets or bodies and sintering them at high temperatures of 1750-1900°C. It has a high volume density, low porosity, and excellent resistance to thermal shock and slag erosion at high temperatures.

[0056] White corundum aggregate is an alumina raw material with an aluminum oxide (Al2O3) content of 97.5% or more, produced by electrolytic melting of industrial alumina as a raw material, and contains trace amounts of iron oxide, silicon oxide, and other components, and is white in color.

[0057] Sub-white corundum aggregate is produced from bauxite and is called sub-white corundum because its chemical composition and physical properties are similar to those of white corundum. It has both the hardness of white corundum and the toughness of brown corundum, making it an ideal high-quality refractory material and abrasive.

[0058] In a preferred specific embodiment of the present invention, the fine powder contains an Al2O3-CaO-MgO-based fine powder and a ZrO2-containing fine powder, and preferably, the Al2O3-CaO-MgO-based fine powder accounts for 50% to 100% by mass and the ZrO2-containing fine powder accounts for 0 to 50% by mass, Preferably, the Al2O3-CaO-MgO-based fine powder comprises an Al2O3-containing fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8, and MgO-CaO-based fine powders; Preferably, the MgO-CaO-based fine powder is an MgO-containing fine powder and / or a CaO-containing fine powder, Preferably, the Al2O3-containing fine powder is one or more fine powders selected from activated α-Al2O3 fine powder, γ-Al2O3 fine powder, ρ-Al2O3 fine powder, aluminum hydroxide fine powder, industrial alumina fine powder, white corundum fine powder, sintered corundum fine powder, and plate-like corundum fine powder; Preferably, the MgO-containing fine powder is one or more fine powders selected from magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, high-purity magnesia, and electrofused magnesia; Preferably, the CaO-containing fine powder is one or more selected from quicklime, limestone, calcium hydroxide, CaO·Al2O3, CaO·2Al2O3 (CA2), 12CaO·7Al2O3 (C12A7), CA6, C2M2A14, and CM2A8; Preferably, the ZrO2-containing fine powder is one or more selected from the group consisting of fine monoclinic zirconia powder, fine tetragonal zirconia powder, fine desiliconized zirconia powder, and fine electrofused zirconia powder.

[0059] After high-temperature hot-press sintering, the Al2O3-CaO-MgO-based fine powder contains corundum and one or more of CA6, CMA8, and C2M2A14. This means that the corundum phase can be converted from Al2O3-containing fine powder at high temperatures. CA6 can be obtained by reacting CA6 fine powder and / or Al2O3-containing fine powder in a CaO-containing raw material with CaO-containing raw materials such as quicklime, limestone, calcium hydroxide, CaO·Al2O3, CaO·2Al2O3, and 12CaO·7Al2O3. C2M2A14 can be obtained by reacting C2M2A14 fine powder and / or Al2O3-containing fine powder, MgO-containing fine powder, or CaO-containing fine powder (excluding C2M2A14). CM2A8 can be obtained by reacting CM2A8 fine powder and / or Al2O3-containing fine powder, MgO-containing fine powder, or CaO-containing fine powder (excluding CM2A8).

[0060] As a mass percentage of the fine powder, the Al2O3-CaO-MgO-based fine powder may be, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any range therebetween. The ZrO2-containing fine powder may be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any range therebetween.

[0061] The Al2O3-containing fine powder means a fine powder whose chemical composition is mainly Al2O3 or Al(OH)3.

[0062] The MgO-containing fine powder refers to a fine powder whose chemical composition is mainly MgO or Mg(OH)2.

[0063] The CaO-containing fine powder means a fine powder containing a CaO component in its chemical composition, or a fine powder containing CaO and Al2O3, or a fine powder containing CaO, MgO and Al2O3.

[0064] The ZrO2-containing fine powder refers to a fine powder whose chemical composition is mainly ZrO2.

[0065] Activated α-Al2O3 fine powder refers to a highly active alumina powder containing α-Al2O3 as the main component, which is obtained by treating raw materials such as industrial alumina or aluminum hydroxide at 1250 to 1450°C.

[0066] γ-Al2O3 fine powder is an alumina powder with a large specific surface area and excellent adsorption properties, which is obtained by processing aluminum hydroxide as a raw material.

[0067] ρ-Al2O3 fine powder is an alumina powder with a certain degree of hydration bonding, obtained by rapid high-temperature treatment at 600 to 900°C using aluminum hydroxide as a raw material.

[0068] Industrial alumina is a mineral whose main component is α-Al2O3, and is obtained by firing aluminum hydroxide at 900 to 1250°C.

[0069] White corundum fine powder is an alumina raw material produced by electromelting industrial alumina as a raw material, and has an aluminum oxide (Al2O3) content of 97.5% or more. It also contains small amounts of iron oxide, silicon oxide, and other components, and is white in color.

[0070] Sintered corundum fine powder refers to a refractory clinker made by crushing alumina into pellets or bodies and sintering them at high temperatures of 1750 to 1900°C. It has a high volume density, low porosity, and excellent resistance to thermal shock and slag erosion at high temperatures.

[0071] Tabular corundum aggregate It has a coarse and well-developed α-Al2O3 crystal structure, an Al2O3 content of more than 97.0%, a plate-like crystal structure, small pores and many closed pores.

[0072] Light-burned magnesia is a highly active magnesia with a periclase phase, obtained by firing magnesite (main component is magnesium carbonate) at 800-1000°C. It is a Gnesian raw material.

[0073] Brucite is a raw material whose main component is Mg(OH)2.

[0074] Sintered magnesia is a dense magnesia raw material that is made by firing light-burned magnesia at high temperatures and has an MgO content of 94.5% or more.

[0075] Electrofused magnesia is a dense magnesia raw material with an MgO content of 96.5% or more, produced by arc melting light-burned magnesia or magnesite as raw material.

[0076] The quicklime, also known as burnt lime, is composed primarily of calcium oxide and is typically produced by burning natural rock, which is primarily composed of calcium carbonate, at high temperatures to decompose it into carbon dioxide and calcium oxide (chemical formula: CaO, i.e., quicklime, also known as marble).

[0077] Monoclinic zirconia is a crystalline form of zirconia that is stable at room temperature, and includes monoclinic crystalline forms.

[0078] Tetragonal zirconia is zirconia stabilized in the tetragonal phase.

[0079] Desiliconized zirconia is zirconia obtained by removing SiO2 and other substances from zircon sand.

[0080] Electrofused zirconia is zirconia produced by arc melting zirconia powder.

[0081] In a preferred specific embodiment of the present invention, the hot-press sintering is carried out by putting the mixed material into a mold of a high-temperature device and hot-press sintering, or by molding the mixed material at room temperature and then putting it into a mold of a high-temperature device and hot-press sintering, or by molding the mixed material at room temperature and then sintering it in a low-temperature device and then putting it into a mold of a high-temperature device and hot-press sintering.

[0082] For example, putting the mixed materials into a mold of a high-temperature device and hot-press sintering means putting the mixed materials into a mold of a high-temperature device, heating them, and once the temperature reaches the maximum, applying pressure to sinter them, or keeping the temperature and pressure for a certain period of time to complete the hot-press sintering of the materials; or putting the mixed materials into a mold of a high-temperature device, heating them to a certain temperature, applying pressure, and then gradually increasing the temperature and pressure until the maximum temperature and pressure reach their maximum, to complete the hot-press sintering of the materials, or keeping the temperature and pressure for a certain period of time to complete the hot-press sintering of the materials; or putting the mixed materials into a mold of a high-temperature device, gradually increasing the pressure applied to the mixed materials while heating them until the temperature reaches their maximum, to complete the hot-press sintering of the materials, or keeping the temperature and pressure for a certain period of time to complete the hot-press sintering of the materials.

[0083] The mixed material is molded at room temperature and then placed in a mold of a high-temperature device for hot-press sintering. This means that the mixed material is pressed at room temperature to form a body, which is then dried and then hot-press sintered; or the body is heated to the maximum temperature and then pressed and sintered, or the temperature and pressure are maintained for a certain period of time to complete the hot-press sintering of the material; or the body is placed in a mold of a high-temperature device and heated to a certain temperature and then pressed, and then the temperature is increased gradually and the pressure is increased until the maximum temperature and pressure are reached, to complete the hot-press sintering of the material, or the temperature and pressure are maintained for a certain period of time to complete the hot-press sintering of the material; or the body is placed in a mold of a high-temperature device and the temperature is increased gradually and the pressure applied to the mixed material is increased until the temperature and pressure are reached, to complete the hot-press sintering of the material, or the temperature and pressure are maintained for a certain period of time to complete the hot-press sintering of the material.

[0084] The high-temperature device is a high-temperature device commonly used by those skilled in the art, such as a high-temperature furnace.

[0085] The mixed material is molded at room temperature, pre-sintered at a low temperature, and then placed in a mold of a high-temperature device for hot-press sintering, which refers to the mixed material being press-molded at room temperature, pre-sintered at 1350-1500°C, and then placed in a mold of a high-temperature device for hot-press sintering. The hot-press sintering operation is the same as above.

[0086] In a preferred specific embodiment of the present invention, the hot press sintering temperature is 1550 to 1800° C., and the hot press strength is preferably 0.5 to 30 MPa.

[0087] The hot press strength is the value of pressure applied to a sample per unit area.

[0088] For example, the temperature may be 1550°C, 1600°C, 1650°C, 1700°C, 1750°C, 1800°C, or any range therebetween; The hot press strength may be, for example, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, 10.5 MPa, 11 MPa, 11.5 MPa, 12 MPa, 12.5 MPa, 13 MPa, 13.5 MPa, 14 MPa, 14.5 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa, or any range therebetween.

[0089] The present invention provides aggregate and fine powder to obtain a mixed material, and hot-press sintering the mixed material to obtain a refractory material. The present invention provides a method for producing the refractory material, comprising:

[0090] In a preferred specific embodiment of the present invention, aggregate and the fine powder have a mass ratio of 30-65:35-70.

[0091] In a preferred specific embodiment of the present invention, the particle size of the fine powder is 0.088 mm or less, and preferably aggregate The particle size is 0.088 Larger than mm 10mm below and preferably 0.088 Larger than mm It is less than 8mm.

[0092] In a preferred specific embodiment of the present invention, the hot-press sintering is carried out by placing the mixed material in a mold of a high-temperature device and hot-press sintering, or by molding the mixed material at room temperature and then placing it in a mold of a high-temperature device and hot-press sintering, or by molding the mixed material at room temperature and then sintering it in a low-temperature device and then placing it in a mold of a high-temperature device and hot-press sintering.

[0093] The present invention utilizes high temperature and pressure to promote granular rearrangement and particle diffusion, and the resulting refractory material has little high-temperature liquid phase, a uniform structure, and excellent thermal shock stability.

[0094] The present invention provides a working lining for a ladle for refining molten steel, comprising the above-mentioned refractory material or a refractory material manufactured by the above-mentioned manufacturing method.

[0095] The present invention provides a working lining for smelting molten aluminum and transporting a ladle, comprising the above-mentioned refractory material or a refractory material manufactured by the above-mentioned manufacturing method.

[0096] The present invention provides a refractory lining for an industrial furnace, which comprises the above-mentioned refractory material or a refractory material produced by the above-mentioned production method. [Example]

[0097] The present invention generally and / or specifically describes the materials and test methods used in the tests. In the following examples, unless otherwise specified, % stands for weight %, i.e., mass percentage. Unless the manufacturer of the reagents or equipment used is specified, they are all commercially available conventional reagent products. Here, Table 1 shows the sources of the raw materials used in the examples.

[0098] [Table 1]

[0099] Example 1 (1) White corundum aggregate 600g of cellulose acetate, 40g of activated α-Al2O3 fine powder, 100g of industrial alumina fine powder, 60g of CM2A8 fine powder, and 200g of electrofused zirconia fine powder were mixed uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold in a high-temperature device and hot-pressed and sintered. When the temperature reached a maximum of 1640°C, pressure was applied, resulting in a maximum hot-press strength of 6 MPa, and a corrosion-resistant refractory material was obtained. The obtained refractory material was analyzed by XRD (powder X-ray diffraction). The sample was polished to 325 mesh or less and then scanned using an X-ray diffractometer (Bruker: D8ADVANCE). The diffraction data was analyzed and compared with a standard PDF card to identify the relevant phases. The diffraction data was then fitted to obtain the contents of the relevant phases. The resulting phases were primarily corundum, CM2A8, and zirconia. The total mass percentage of the refractory material's phases was 99.1%, with the corundum phase accounting for 73.1%, the CM2A8 phase accounting for 6.0%, and the zirconia phase accounting for 20.0%. The refractory material was analyzed by XRF according to the standard and measured in accordance with GB / T 21114-2007, and the resulting refractory material contained, as mass percentages of the refractory material, 78.17% Al2O3, 0.43% MgO, 0.35% CaO, and 20.0% ZrO2. The refractory material of this example was measured in accordance with GB / T2997-2000 and found to have a bulk density of 3.30 g / cm 3 It was.

[0100] Example 2 (1) Dense corundum aggregate 300g, tabular corundum aggregate200g, 140g of CA6 fine powder, 92g of industrial alumina fine powder, 15g of 8.4g of CaCO3 fine powder, 160g of white corundum powder, and 100g of desiliconized zirconia fine powder were stirred uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold in a high-temperature device and hot-pressed and sintered. When the temperature reached 1500°C, pressure was applied, and the pressure was increased as the temperature increased. The maximum temperature reached 1760°C, and the maximum hot-press strength reached 2 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum, CA6, and zirconia, and the total amount of corundum, CA6, and zirconia, as measured as mass percentages in the phases of the refractory material, was 98.18%, with the corundum phase accounting for 65.1%, the CA6 phase for 23.4%, and the zirconia phase for 9.68%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in mass percentages relative to the refractory material, 87.12% Al2O3, 1.93% CaO, and 9.65% ZrO2. When measured in the same manner as in Example 1, the volume density obtained was 3.12 g / cm 3 It was.

[0101] Example 3 (1) Sub-white corundum aggregate 260g, CM2A8 aggregate 140g of ammonium hydroxide, 60g of white corundum powder, 100g of CM2A8 powder, 17g of fine C12A7 powder, 17.5g of magnesium hydroxide powder, 113g of activated α-Al2O3 powder, and 300g of electrofused zirconia powder were mixed together and stirred uniformly. aggregate The maximum particle size was 8 mm. (2) The mixed material was press-molded and dried, then placed in a mold in a high-temperature device and hot-pressed and sintered. The maximum temperature was 1780°C and the maximum hot-press strength was 0.5 MPa, resulting in a corrosion-resistant refractory material. Analysis by the same method as in Example 1 revealed that the obtained phases were mainly corundum, CM2A8, and zirconia, and the total amount of corundum, CM2A8, and zirconia, as measured as mass percentages in the phases of the refractory material, was 98.5%, with the corundum phase accounting for 32.0%, the CM2A8 phase accounting for 36.5%, and the zirconia phase accounting for 30%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, as mass percentages in the refractory material, 64.57% Al2O3, 2.94% MgO, 2.01% CaO, and 30% ZrO2. When measured in the same manner as in Example 1, the volume density obtained was 3.30 g / cm 3 It was.

[0102] Example 4 (1) Sintered corundum aggregate 300g, dense corundum aggregate 300 g of ammonium hydroxide, 280 g of fine white corundum powder, 110 g of activated α-Al2O3 powder, and 13.5 g of fine calcium hydroxide powder were mixed together to homogeneity. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold in a high-temperature device and hot-pressed and sintered. When the temperature rose to 1400°C, pressure was gradually applied until the maximum temperature reached 1680°C and the maximum hot-press strength reached 1 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages in the measured phases of the refractory material was 98.6%, with the corundum phase accounting for 88.0% and the CA6 phase accounting for 10.6%. When analyzed in the same manner as in Example 1, the obtained refractory material was found to contain, in terms of mass percentage in the refractory material, 98.99% Al2O3 and 0.89% CaO. When measured in the same manner as in Example 1, the volume density obtained was 2.95 g / cm 3 It was.

[0103] Example 5 (1) Sub-white corundum aggregate500g, 73g of CA6 fine powder, 100g of white corundum powder, 28g of ρ-Al2O3 powder, and 40g of CaO·Al2O3 fine powder were mixed uniformly. aggregate The maximum particle size was 5 mm. (2) An appropriate amount of water was added to the mixed material and stirred uniformly, then cast and molded, dried, and then pre-fired at 1500°C before being placed in a mold in a high-temperature device and hot-pressed for sintering. When the temperature rose to 1770°C, pressure was applied, and the maximum hot-press strength reached 2 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages of the measured phases of the refractory material was 96.9%, with the corundum phase accounting for 74.5% and the CA6 phase accounting for 22.4%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 96.9% Al2O3 and 1.95% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.12 g / cm 3 It was.

[0104] Example 6 (1) Tabular corundum aggregate 650 g of the powder, 105 g of CA6 fine powder, 100 g of white corundum powder, and 223 g of aluminum hydroxide powder were stirred uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold in a high-temperature device and hot-pressed and sintered. The temperature and pressure were increased until the maximum temperature reached 1700°C and the maximum hot-press strength reached 14 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages in the measured phases of the refractory material was 98.1%, the corundum phase was 88.0%, and the CA6 phase was 10.1%. When analyzed in the same manner as in Example 1, the obtained refractory material was found to contain, in terms of mass percentage in the refractory material, 98.99% Al2O3 and 0.75% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.28 g / cm 3 It was.

[0105] Example 7 (1) Sub-white corundum aggregate 500g of molten aluminum, 100g of C2M2A14 fine powder, 45g of CA2 fine powder, 7g of electrofused magnesia powder, 89g of ρ-Al2O3 powder, and 260g of white corundum powder were mixed uniformly. aggregate The maximum particle size was 5 mm. (2) An appropriate amount of water was added to the mixed material and stirred uniformly, followed by vibration molding. After drying, the material was pre-fired at 1350°C and then placed in a mold in a high-temperature device for hot-press sintering. When the temperature rose to 1750°C, pressure was applied, and the maximum hot-press strength reached 1 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and C2M2A14, and the total amount of corundum and C2M2A14 in terms of mass percentages of the measured phases of the refractory material was 96.2%, with the corundum phase accounting for 75.0% and the C2M2A14 phase accounting for 21.2%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in mass percentages relative to the refractory material, 96.3% Al2O3, 1.0% MgO, and 1.20% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.12 g / cm 3 It was.

[0106] Example 8 (1) Sub-white corundum aggregate 300g of ammonium hydroxide, 90g of fine powder of CA6, 17g of fine powder of calcium hydroxide, 138g of activated α-Al2O3 powder, 265g of ρ-Al2O3 powder, and 460g of white corundum powder were mixed uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was press-molded and dried, then placed in a high-temperature device and treated at 1450°C. The treated sample was placed in a mold in the high-temperature device and hot-pressed and sintered. When the temperature reached 1600°C, pressure was applied, and the pressure was increased as the temperature increased. The maximum temperature was 1770°C, and the maximum hot-press strength was 3 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages of the measured phases of the refractory material was 97.1%, with the corundum phase accounting for 74.7% and the CA6 phase accounting for 22.4%. When analyzed in the same manner as in Example 1, the obtained refractory material contained 96.4% Al2O3 and 1.91% CaO, as mass percentages in the refractory material. When measured in the same manner as in Example 1, the volume density obtained was 3.12 g / cm 3 It was.

[0107] Example 9 (1) Tabular corundum aggregate 500g of CM2A8 fine powder, 100g of CM2A8 fine powder, 11g of calcium hydroxide fine powder, 17.5g of high purity magnesia powder, 122g of industrial alumina fine powder, and 260g of plate-like corundum powder were stirred uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was molded at room temperature and dried, then placed in a mold in a high-temperature device and hot-pressed for sintering. When the temperature reached 1550°C, pressure was applied, and the pressure was increased while the temperature was raised until the maximum temperature reached 1740°C, at which point the maximum hot-press strength reached 4 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CM2A8, and the total amount of corundum and CM2A8 in terms of mass percentages in the measured phases of the refractory material was 95.42%, with the corundum phase accounting for 73.1% and the CM2A8 phase accounting for 22.32%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in mass percentages relative to the refractory material, 95.7% Al2O3, 1.97% MgO, and 1.02% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.12 g / cm 3 It was.

[0108] Example 10 (1) Sintered corundum aggregate 260g, CA6 aggregate 140 g of granular granules, 120 g of fine off-white corundum powder, 55 g of fine Ca(OH)2 powder, 200 g of platy corundum powder, and 245 g of fine ρ-Al2O3 powder were mixed uniformly. aggregate The maximum particle size was 6 mm. (2) The mixed material was press-molded at room temperature and pre-fired at 1500°C. It was then placed in a mold in a high-temperature device and pressure was applied while the temperature was increased. The maximum temperature rose to 1750°C, and the maximum hot press strength was 7 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages in the measured phases of the refractory material was 98.8%, the corundum phase was 36.8%, and the CA6 phase was 62.0%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 93.7% Al2O3 and 5.20% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.25 g / cm 3 It was.

[0109] Example 11 (1) Tabular corundum aggregate 195g, CM2A8 aggregate 105g of activated α-Al2O3 powder, 70g of activated α-Al2O3 powder, 280g of fine CM2A8 powder, 100g of fine tetragonal zirconia powder, and 250g of fine electrofused zirconia powder were mixed together and stirred uniformly. aggregate The maximum particle size was 5 mm. (2) After molding the mixed material at room temperature, it was placed in a mold in a high-temperature device and hot-pressed and sintered. Pressure was applied while the temperature was increased, and the maximum temperature rose to 1550°C, with a maximum hot-press strength of 30 MPa, resulting in a corrosion-resistant refractory material. Analysis by the same method as in Example 1 revealed that the obtained phases were mainly corundum, CM2A8, and zirconia, and the total amount of corundum, CM2A8, and zirconia, as measured as mass percentages in the phases of the refractory material, was 99.6%, with the corundum phase accounting for 26.5%, the CM2A8 phase accounting for 38.1%, and the zirconia phase accounting for 35%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, as mass percentages in the refractory material, 59.5% Al2O3, 3.01% MgO, 2.03% CaO, and 35% ZrO2. When measured in the same manner as in Example 1, the volume density obtained was 3.45 g / cm 3 It was.

[0110] Example 12 (1) Sub-white corundum aggregate 350g, sintered corundum aggregate 300 g of the zirconia powder, 175 g of fine monoclinic zirconia powder, 52.5 g of fine CM2A8 powder, and 188 g of aluminum hydroxide powder were mixed together and uniformly stirred. aggregate The maximum particle size was 3 mm. (2) The mixed material was placed in a mold in a high-temperature furnace and hot-pressed and sintered. When the temperature reached 1350°C, pressure was applied, and the pressure was increased while the temperature was being increased. The maximum temperature reached 1600°C, and the maximum hot-press strength reached 15 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum, CM2A8, and zirconia, and the total amount of corundum, CA6, and zirconia, as measured mass percentages in the phases of the refractory material, was 97.15%, with the corundum phase accounting for 75.4%, the CM2A8 phase accounting for 5.25%, and the zirconia phase accounting for 16.5%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, as mass percentages in the refractory material, 80.8% Al2O3, 0.30% CaO, 0.43% MgO, and 16.9% ZrO2. When measured in the same manner as in Example 1, the volume density obtained was 3.26 g / cm 3 It was.

[0111] Example 13 (1) Sintered corundum aggregate 195g, CA6 aggregate 105g of ammonium hydroxide, 100g of industrial fine alumina powder, 138.5g of ρ-Al2O3 powder, 460g of CA6 fine powder, and 11.5g of calcium hydroxide powder were mixed together and homogeneously stirred. aggregate The maximum particle size was 8 mm. (2) The mixed material was molded and dried at room temperature, then heated to 1500°C and placed in a mold in a high-temperature device for hot-press sintering. The maximum temperature was 1700°C, and the maximum hot-press strength was 21 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages of the measured phases of the refractory material was 97.7%, the corundum phase was 31.2%, and the CA6 phase was 66.5%. When analyzed in the same manner as in Example 1, the obtained refractory material contained 93.1% Al2O3 and 5.58% CaO, in terms of mass percentage in the refractory material. When measured in the same manner as in Example 1, the volume density obtained was 3.25 g / cm 3 It was.

[0112] Example 14 (1) Sintered corundum aggregate 300g of ammonium hydroxide, 460g of industrial alumina fine powder, 140g of CA6 fine powder, 11.5g of calcium hydroxide powder, and 93g of γ-Al2O3 powder were mixed together and stirred uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold in a high-temperature device and hot-pressed. The maximum temperature was 1650°C, and the maximum hot-press strength was 8 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages of the measured phases of the refractory material was 95.4%, the corundum phase was 75.1%, and the CA6 phase was 20.3%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 96.1% Al2O3 and 1.94% CaO. When measured in the same manner as in Example 1, the volume density obtained was 2.90 g / cm 3 It was.

[0113] Example 15 (1) Sintered corundum aggregate 260g, CM2A8 aggregate 140 g of ammonium hydroxide, 40 g of industrial fine alumina powder, 83 g of ρ-Al2O3 powder, and 480 g of CM2A8 fine powder were mixed together to homogeneity. aggregate The maximum particle size was 10 mm. (2) The mixed material was placed in a mold in a high-temperature furnace and hot-pressed. The maximum temperature was 1650°C, and the maximum hot-press strength was 4 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CM2A8, and the total amount of corundum and CM2A8 in terms of mass percentages in the measured phases of the refractory material was 98.8%, with the corundum phase accounting for 36.8% and the CM2A8 phase accounting for 62%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in mass percentages relative to the refractory material, 90.1% Al2O3, 5.20% MgO, and 3.60% CaO. When measured in the same manner as in Example 1, the volume density obtained was 2.90 g / cm 3 It was.

[0114] Example 16 (1) Sintered corundum aggregate 195g, CM2A8 aggregate 105g of cellulose acetate, 100g of industrial fine alumina powder, 40g of ρ-Al2O3 powder, and 560g of CM2A8 fine powder were mixed together and homogeneously stirred. aggregate The maximum particle size was 1 mm. (2) The mixed material was placed in a mold in a high-temperature furnace and directly hot-pressed. The maximum temperature was 1800°C, and the hot-press strength was 2 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CM2A8, and the total amount of corundum and CM2A8 in terms of mass percentages in the measured phases of the refractory material was 98.3%, with the corundum phase accounting for 31.8% and the CM2A8 phase accounting for 66.5%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 89.3% Al2O3, 5.58% MgO, and 3.88% CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.65 g / cm 3 It was.

[0115] Example 17 (1) 300 g of sintered corundum particles, 585 g of industrial alumina fine powder, 40 g of ρ-Al2O3 fine powder, 45 g of calcium hydroxide fine powder, and 48 g of electrofused magnesia were stirred uniformly. aggregate The maximum particle size was 1 mm. (2) The mixed material was molded at room temperature, dried, and then treated at 1450°C. It was then placed in a mold in a high-temperature device and hot-pressed and sintered. The maximum temperature was 1720°C, and the hot-press strength was 3 MPa, resulting in a corrosion-resistant refractory material. Analysis was performed in the same manner as in Example 1, and the obtained phases were mainly corundum, CM2A8, and CA6. As mass percentages of the measured phases of the refractory material, the total amount of corundum and CM2A8 was 90.0%, the corundum phase was 44.0%, the CM2A8 phase was 22.6%, and the CA6 phase was 23.4%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 90.8% Al2O3, 4.28% MgO, and 3.13% CaO. When measured in the same manner as in Example 1, the volume density obtained was 2.93 g / cm 3 It was.

[0116] Example 18 (1) 650 g of white corundum aggregate, 105 g of CA6 fine powder, and 250 g of white corundum powder were mixed uniformly. aggregate The maximum particle size was 5 mm. (2) The mixed material was placed in a mold of a high-temperature device and hot-pressed and sintered. The temperature and pressure were increased until the maximum temperature reached 1715°C, and the maximum hot-press strength was 7.5 MPa, resulting in a corrosion-resistant refractory material. Analysis in the same manner as in Example 1 revealed that the obtained phases were mainly corundum and CA6, and the total amount of corundum and CA6 in terms of mass percentages of the measured phases of the refractory material was 99.53%, with the corundum phase accounting for 89.50% and the CA6 phase accounting for 10.3%. When analyzed in the same manner as in Example 1, the obtained refractory material contained, in terms of mass percentage in the refractory material, 98.99% Al2O3 and 0.84% ​​CaO. When measured in the same manner as in Example 1, the volume density obtained was 3.25 g / cm 3 It was.

[0117] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 employed a conventional manufacturing method, that is, the method of Example 1 in Chinese Patent Publication No. CN107500747A, to obtain the refractory material. When analyzed in the same manner as in Example 1, the chemical composition of the obtained refractory material was found to contain, as a mass percentage in the refractory material, 92.11% Al2O3 and 7.02% CaO. Analysis by the same method as in Example 1 revealed that the phases of Comparative Example 1 were mainly CA6, corundum, CaO·Al2O3, and CaO·2Al2O3, and the mass percentages of the phases in the refractory material were 69.1% for the CA6 phase, 24.2% for the corundum phase, 2.30% for the CaO·Al2O3 phase, and 2.31% for the CaO·2Al2O3 phase. When measured in the same manner as in Example 1, the volume density of Comparative Example 1 was 3.05 g / cm 3 It was.

[0118] [Table 2-1]

[0119] [Table 2-2]

[0120] Experimental Example 1 Dynamic slag erosion test In the dynamic slag erosion test, the refractory material obtained in Example 1 and the refractory material sample obtained in Comparative Example 1 were compared. The samples for dynamic slag erosion must be long enough to be fixed to a rotating shaft. The refractory material obtained in Example 1 had a high volume density, a high corundum content, and high hardness, making it difficult to grind into a cylindrical sample with a diameter of 15 mm. Instead, it had to be cut into a square bar. The erosion rate was measured based on the size of the opposite side, so cutting the sample into a square bar did not affect the accuracy of the final results. For comparison, the castable material of Comparative Example 1 was injection cast into a sample of the same size. The conditions for the dynamic slag corrosion test were as follows: deoxidation using metallic aluminum, the experimental temperature was 1600°C, the atmosphere was argon, the slag system used was CaO-Al2O3-SiO2, and the steelmaking slag composition was CaO 51%, Al2O3 30%, SiO2 11%, MgO 8%, and CaO / SiO2 4.6. The castable of Comparative Example 1 and the refractory material described in Example 1 were each attached to a motor with a high-temperature adhesive, and the rotation speed was controlled at 10 cycles / min. The experimental results are shown in Figures 1A and 1B, respectively. 1A and 1B, after 8 minutes of rotation, the castable sample of Comparative Example 1 immersed in steelmaking slag collapsed, whereas the refractory material of Example 1 showed almost no change, retaining very high roundness and essentially remaining unchanged. The sample was cut open and the width of the unreacted interface was measured with a vernier caliper. Damage of 0.2 to 0.5 mm was found, indicating that the refractory material obtained in Example 1 had excellent corrosion resistance.

[0121] Experimental example 2: Static slag erosion test The crucible method was used for the static slag erosion test. Figure 2A shows a schematic diagram of the static crucible method for molten steel refining. The refractory material of Example 1 was hot-pressed into a 45 mm diameter sample, and then a 30 mm × 40 mm pit was drilled into the sample. The castable material of Comparative Example 1 was injection-cast into a 45 mm diameter sample, with an internal pit measuring 30 mm × 40 mm. The test conditions were 1600°C, argon atmosphere, and deoxidation with metallic aluminum. The slag system used was a CaO-Al2O3-SiO2 system, with a steelmaking slag composition of 51% CaO, 30% Al2O3, 11% SiO2, 8% MgO, and 4.6% CaO / SiO2. The static slag erosion results are shown in Figure 2B. Here, a, b, and c represent the profile structures of the castable material of Comparative Example 1 at 30, 40, and 50 minutes, respectively, and d, e, and f represent the profile structures of the sample of Example 1 at 30, 40, and 50 minutes, respectively. As can be seen from Figure 2B, after 40 minutes, the castable of Comparative Example 1 was completely infiltrated and eroded by the slag in some areas, resulting in the sample's collapse. The erosion thickness in some areas was 270 μm, but the slag had completely infiltrated the sample. This is caused by the structure and properties of conventional refractory materials. Conventional materials often have an uneven structure, so while they are generally good overall, some areas are no longer durable. In contrast, the sample of Example 1 of the present invention showed very good uniformity and a very complete structure. Furthermore, Figure 2C is a comparison of the microstructure of the castable of Comparative Example 1 with that of the sample of Example 1 of the present invention, where a, b, and c are the microstructures of the castable of Comparative Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively, and d, e, and f are the microstructures of the sample of Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively. The microstructure shows that the structure of the castable of Comparative Example 1 is very uneven, and slag may penetrate deeply along the more porous areas, while the metamorphic layer of Example 1 of the present invention is very thin and uniform. This also indicates the superior performance of the sample of the present invention.

[0122] Experimental Example 3: Slag corrosion and thermal shock stability test The refractories obtained in Examples 1 to 17 and Comparative Example 1 were subjected to slag erosion and thermal shock stability tests. To measure the slag erosion status, the crucible after the experiment was first cut along the midplane, samples were taken from the crucible wall, and the slag erosion status was determined by observing and measuring the samples under an electron microscope. The thermal shock stability test was performed in accordance with GB / T 30873-2014, and the results are shown in Table 3.

[0123] [Table 3]

[0124] The applicability and performance evaluation of refractory materials is not only related to slag corrosion resistance, but also the thermal shock stability of the refractory material under rapid cooling and heating conditions must be considered. If the thermal shock stability is poor, cracks may occur during use, which may affect the performance of the material.

[0125] In terms of corrosion resistance, under the same volume density, the addition of ZrO2 is advantageous, and corundum has better corrosion resistance than CA6, C2M2A8, and CM2A8. For the same composition, refractory materials with higher volume density have better corrosion resistance.

[0126] In terms of thermal shock stability, the addition of ZrO2 is advantageous, and the addition of CA6 has better thermal shock stability than refractory materials with the same mass of corundum, C2M2A8, and CM2A8 added. With the same composition, if the volume density is small, the thermal shock stability is relatively good.

[0127] It is also necessary to consider the cost performance of the refractory material. For example, refractory materials containing zirconia have excellent slag corrosion resistance and thermal shock stability, and even when added in large amounts, their performance remains excellent. However, since zirconia is expensive, the examples of the present invention are based on a comprehensive comparison of their performance.

[0128] The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention to other forms, and those skilled in the art can use the technical content disclosed above to change or modify the above into equivalent embodiments with equivalent changes, however, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. 1. A corrosion-resistant refractory material, the phases of which are corundum, CA6, C2M2A14, CM2A8, and ZrO ２ and one or more phases selected from the total content of corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO 2 is 90% or more as a mass percentage of the phases of the refractory material; The content of the corundum phase is 26.5 to 89.5%, The total content of CA6+C2M2A14+CM2A8 phase is 5.25 to 66.5%, The content of ZrO 2 phase is 0 to 35%, The content of impurity components that promote sintering is 1.5% or less as a mass percentage in the refractory material, The refractory material is manufactured by a method including the steps of mixing aggregate and fine powder to obtain a mixed material, and hot-pressing and sintering the mixed material to obtain the refractory material; The refractory material has a mass ratio of the aggregate to the fine powder of 30 to 65:35 to 70.

2. The content of the corundum phase as a mass percentage of the phase of the refractory material is 32 to 89.5%, The total content of CA6+C2M2A14+CM2A8 phase is 5.25 to 62.0%, Refractory material according to claim 1, wherein the content of ZrO2 phase is 0 to 30%.

3. 2. The refractory material according to claim 1, wherein the content of impurity components that promote sintering is 1.0% or less by mass percentage in the refractory material.

4. The chemical composition of the refractory material is Al ２ O ３ and CaO, optionally containing MgO, ZrO ２ and optionally containing, as a mass percentage in the refractory material, ２ O ３ 2. The refractory material according to claim 1, wherein the content of CaO is 59.5 to 98.99%, the content of CaO is 0.30 to 5.58%, and the content of MgO is 0 to 5.58%.

5. The fire-resistant material according to claim 1, wherein the volume density of the fire-resistant material is 2.90 to 3.65 g / cm 3 .

6. The fire-resistant material described in claim 1, wherein the aggregate comprises corundum aggregate and optionally mixed aggregate.

7. 2. The fireproof material according to claim 1, wherein the particle size of the fine powder is 0.088 mm or less, and the particle size of the aggregate is more than 0.088 mm and 10 mm or less.

8. 2. The refractory material according to claim 1, wherein the hot-press sintering is performed by placing the mixed material in a mold of a high-temperature device and hot-press sintering the mixed material, or by molding the mixed material at room temperature and then placing it in a mold of a high-temperature device and hot-press sintering the mixed material, or by molding the mixed material at room temperature and then pre-sintering it at a low temperature and then hot-press sintering the mixed material.

9. A method for producing the refractory material, comprising the steps of: mixing aggregate and fine powder to obtain a mixed material; and then hot-pressing and sintering the mixed material to obtain a refractory material, The mass ratio of the aggregate to the fine powder is 30 to 65:35 to 70, the refractory material is a corrosion-resistant refractory material, and the phases of the refractory material include corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO 2 ; the total content of corundum and one or more phases selected from CA6, C2M2A14, CM2A8, and ZrO 2 is 90% or more as a mass percentage of the phases of the refractory material; The content of the corundum phase is 26.5 to 89.5%, The total content of CA6+C2M2A14+CM2A8 phase is 5.25 to 66.5%, The content of ZrO 2 phase is 0 to 35%, The manufacturing method, wherein the content of impurity components that promote sintering is 1.5% or less as a mass percentage in the refractory material.

10. The manufacturing method according to claim 9, wherein the particle size of the fine powder is 0.088 mm or less, and the particle size of the aggregate is more than 0.088 mm and 10 mm or less.

11. 10. The manufacturing method according to claim 9, wherein the hot-press sintering is performed by placing the mixed material in a mold of a high-temperature device and hot-press sintering the mixed material, or by molding the mixed material at room temperature and then placing it in a mold of a high-temperature device and hot-press sintering the mixed material, or by molding the mixed material at room temperature, pre-sintering it at a low temperature, and then placing it in a mold of a high-temperature device and hot-press sintering the mixed material.

12. A working lining for a ladle for refining molten steel, comprising the refractory material according to claim 1 or the refractory material manufactured by the manufacturing method according to claim 9.

13. A working lining for smelting aluminum molten metal and transporting a ladle, comprising the refractory material according to claim 1 or the refractory material manufactured by the manufacturing method according to claim 9.

14. A refractory lining for an industrial furnace, comprising the refractory material according to claim 1 or the refractory material produced by the method according to claim 9.

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