Refractory and method for producing the same, use of the same, refractory brick, and glass melting furnace

Abstract

The application relates to a refractory material and a preparation method, application and refractory brick thereof, and a glass melting furnace. The preparation raw material of the refractory material comprises the following components in parts by mass: 55-80 parts of fused zirconium mullite, 10-15 parts of zirconium oxide powder and 10-30 parts of aluminum oxide powder. The fused zirconium mullite, the aluminum oxide powder and the zirconium oxide powder are synergized through the specific proportion, and after sintering treatment, a crystal phase structure mainly composed of mullite crystals is formed, and there are zirconite phases and eutectoid of corundum and baddeleyite crystals in the crystal phase structure, the crystal phase structures are interwoven together to form a frame structure. Part of the low-melting-point components in the fused zirconium mullite exist in a molten glass phase in the sintering process and are filled between the crystal lattices of various crystal phases, so that the product has a compact structure, the porosity is reduced, and the performance of resisting glass liquid corrosion is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of refractory materials, in particular to a refractory material, a preparation method and application thereof, a refractory brick and a glass melting furnace. BACKGROUND

[0002] The photovoltaic glass industry is currently in a stage of rapid development, and the future development trend is very optimistic. To produce high-quality photovoltaic glass, not only mature process conditions are needed, but also the corresponding production equipment has an important influence on the quality of the glass. For example, the glass melting furnace; its main function is to heat the glass raw materials (such as quartz sand, soda ash, limestone, etc.) to high temperature, so that they are melted and mixed uniformly to form a glass liquid that meets the quality requirements.

[0003] The lip brick is located at the interface of the glass liquid and the furnace gas in the glass melting furnace, that is, the "lip" of the glass melting furnace, which is the edge part of the channel for the glass liquid to enter and exit the melting furnace. The shape of the lip brick is generally long strip, one side is in contact with the glass liquid, and the other side is exposed to the furnace gas; the main function of the lip brick is to control the flow of the glass liquid and guide the glass liquid to enter and exit the melting furnace. The lip brick is generally made of refractory material; at the same time, since the lip brick is in a high-temperature and chemically aggressive environment, it needs to have good corrosion resistance and thermal shock resistance to prevent being eroded by the chemical components in the glass liquid and the furnace gas, so as to ensure the normal operation of the glass melting furnace and the quality of the glass products. In addition, the foaming rate of the lip brick is also a key factor affecting the quality of the glass.

[0004] Therefore, the traditional technology needs to be improved. SUMMARY

[0005] Therefore, it is necessary to provide a refractory material with low foaming rate, good corrosion resistance and good thermal shock resistance, a preparation method and application thereof, a refractory brick and a glass melting furnace.

[0006] The first aspect of the present application provides a refractory material, the preparation raw materials of which comprise the following components in parts by mass: 55-80 parts of fused zirconium mullite, 10-15 parts of zirconia powder, and 10-30 parts of alumina powder.

[0007] The refractory material is prepared by using raw materials containing electrically fused zircon mullite, alumina powder and zirconia powder in specific proportions; the electrically fused zircon mullite has good thermal shock resistance and low porosity, which provides a basis for the low porosity and thermal shock resistance of the refractory material; on this basis, the electrically fused zircon mullite, alumina powder and zirconia powder are synergized in the specific proportions, and after sintering, a crystal phase structure mainly composed of mullite phase, eucolite phase and corundum eutectoid and sphene crystals is formed, these crystal phase structures are interwoven together to form a framework structure, which is conducive to improving the strength and thermal shock resistance of the refractory material. In addition, part of the low-melting-point components in the electrically fused zircon mullite exist in the form of glass phase in the sintering process and fill between the crystal lattices of each crystal phase, so that the product has a compact structure, which is conducive to reducing the porosity and improving the performance of resisting glass liquid corrosion. Thus, a refractory material with low foaming rate, good corrosion resistance and good thermal shock resistance is provided.

[0008] In some embodiments, the refractory material contains a crystal phase including mullite phase, corundum phase, eucolite phase and eucolite phase.

[0009] In some embodiments, in the refractory material, the crystal phase includes 45% to 50% of mullite phase, 17% to 20% of corundum phase, 20% to 23% of eucolite phase and 10% to 13% of eucolite phase in terms of mass content.

[0010] In some embodiments, the refractory material satisfies at least one of the following conditions:

[0011] (1) the porosity of the electrically fused zircon mullite is 16% to 17.5%;

[0012] (2) the components in the electrically fused zircon mullite satisfy the following conditions: the mass fraction of ZrO2 is > 32.5%, the mass fraction of Al2O3 is > 42%, the mass fraction of SiO2 is ≤ 18%, the mass fraction of TiO2 is ≤ 0.2%, the mass fraction of Fe2O3 is ≤ 0.2%, the total mass fraction of Na2O and K2O is ≤ 0.35%, and the total mass fraction of CaO and MgO is ≤ 0.35%;

[0013] (3) the components in the alumina powder satisfy the following conditions: the mass fraction of Al2O3 is > 98.5%, the mass fraction of SiO2 is < 0.3%, the mass fraction of Fe2O3 is ≤ 0.1%, and the total mass fraction of Na2O and K2O is ≤ 0.35%; the loss on ignition of the alumina powder is < 0.5%;

[0014] (4) the components in the zirconia powder satisfy the following conditions: mass fraction of ZrO2> 65.5%, mass fraction of SiO2< 34%, mass fraction of Fe2O3≤ 0.2%, and mass fraction of TiO2≤ 0.35%.

[0015] In some embodiments, the refractory material satisfies at least one of the following conditions:

[0016] (1) the electro-fused zircon mullite includes electro-fused zircon mullite coarse material with a particle size greater than 3 mm and less than or equal to 5 mm, electro-fused zircon mullite medium material with a particle size greater than 1.5 mm and less than or equal to 3 mm, electro-fused zircon mullite fine material with a particle size greater than 0.5 mm and less than or equal to 1.5 mm, electro-fused zircon mullite ultra-fine material with a particle size greater than 0.1 mm and less than or equal to 0.5 mm, and electro-fused zircon mullite micro-powder with a D50 of 10 μm to 20 μm;

[0017] (2) the D50 of the zirconia powder is 5 μm to 15 μm;

[0018] (3) the alumina powder includes alumina powder A with a D50 of 1.5 μm to 2.5 μm and alumina powder B with a D50 of 3 μm to 6 μm.

[0019] In some embodiments, the preparation raw materials include the following by mass fraction:

[0020] the electro-fused zircon mullite coarse material 10 parts to 35 parts,

[0021] the electro-fused zircon mullite medium material 5 parts to 25 parts,

[0022] the electro-fused zircon mullite fine material 3 parts to 15 parts,

[0023] the electro-fused zircon mullite ultra-fine material 15 parts to 25 parts,

[0024] the electro-fused zircon mullite micro-powder 5 parts to 10 parts,

[0025] the alumina powder A 8 parts to 20 parts,

[0026] the alumina powder B 2 parts to 10 parts, and

[0027] the zirconia powder 10 parts to 15 parts.

[0028] In some embodiments, the alumina powder A is composed of 40% to 60% of alumina powder A1 and 40% to 60% of alumina powder A2 by mass percentage; the D50 of the alumina powder A1 is 2 μm ± 0.1 μm; and the D50 of the alumina powder A2 is 2.3 μm ± 0.1 μm.

[0029] In some embodiments, the refractory material satisfies at least one of the following conditions:

[0030] (1) the preparation raw material further comprises 0.2 parts to 0.4 parts of a dispersion enhancer;

[0031] (2) the preparation raw material further comprises 5 parts to 7 parts of water.

[0032] In some embodiments, the dispersion enhancer is an inorganic clay; the inorganic clay satisfies at least one of the following conditions:

[0033] (1) the components in the inorganic clay satisfy the following conditions: mass fraction of Al2O3 < 15%, mass fraction of SiO2 > 50%, mass fraction of CaO ≤ 5%, and mass fraction of MgO ≤ 25%;

[0034] (2) D50 of the inorganic clay is 3 μm to 15 μm;

[0035] (3) the inorganic clay comprises at least one of attapulgite and kaolin.

[0036] In the second aspect of the present application, a preparation method of the above-mentioned refractory material is provided, comprising the following steps:

[0037] mixing the raw material, and then casting forming to obtain a blank;

[0038] calcining the blank to obtain the refractory material.

[0039] In some embodiments, the preparation method satisfies at least one of the following conditions:

[0040] (1) the casting forming adopts vacuum casting forming; the vacuum degree of the vacuum casting forming is -0.08 MPa to -0.1 MPa; the forming pressure is 0.2 MPa to 0.4 MPa;

[0041] (2) before the calcining of the blank, a step of drying the blank is further included;

[0042] the drying step comprises: first naturally airing the blank for 120 h to 240 h, and then baking at 40 °C to 80 °C for 48 h to 96 h;

[0043] (3) the calcining temperature is 1300 °C to 1500 °C; the calcining time is 8 h to 15 h.

[0044] In the third aspect of the present application, the above-mentioned refractory material is provided for preparing a refractory product.

[0045] In a fourth aspect, the present application provides a refractory brick comprising the refractory material according to the first aspect.

[0046] In a fifth aspect, the present application provides a glass melting furnace comprising the refractory brick according to the fourth aspect. BRIEF DESCRIPTION OF DRAWINGS

[0047] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced as follows. Obviously, the drawings in the following description only represent the embodiments of the present application, and other drawings can also be obtained by those skilled in the art without any creative effort on the basis of the disclosed drawings.

[0048] Figure 1 Surface image of the refractory brick prepared for Example 3 after the foaming experiment.

[0049] Figure 2 Surface image of the refractory brick prepared for Comparative Example 1 after the foaming experiment.

[0050] Figure 3 Glass corrosion resistance image of the refractory bricks prepared for Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0051] In order to facilitate the understanding of the present application, the present application will be described more fully below. Preferred embodiments of the present application are given. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. It should be understood that the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein only for the purpose of describing specific embodiments and is not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0053] In the description of the present application, it should be understood that the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise specifically limited.

[0054] The weight of the related components mentioned in the embodiment of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiment of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the embodiment of the present application. Specifically, the weight mentioned in the embodiment of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0055] In an embodiment of the present application, a refractory material is provided, and the preparation raw materials include the following components in parts by mass: 55-80 parts of fused zirconium mullite, 10-15 parts of zirconia powder, and 10-30 parts of alumina powder.

[0056] The refractory material contains fused zirconium mullite, alumina powder and zirconia powder in a specific ratio. The fused zirconium mullite has good thermal shock resistance and low porosity, and the low porosity and thermal shock resistance of the refractory material provide a basis. Moreover, part of the low-melting-point components in the fused zirconium mullite exist in the form of glass phase in the molten state. After sintering treatment of the fused zirconium mullite, alumina powder and zirconia powder in the above specific ratio, a crystal phase structure mainly composed of mullite crystals is formed, followed by zirconite phase and eutectoid of corundum and baddeleyite crystals, which are interwoven together to form a framework structure, thereby improving the strength and thermal shock resistance of the refractory material. Further, the low-melting-point substances in the fused zirconium mullite fill between the crystal lattices of each crystal phase in the form of glass phase, so that the product has a compact structure, low porosity and good resistance to glass liquid corrosion.

[0057] In some embodiments, the refractory material contains a crystal phase including mullite phase, corundum phase, baddeleyite phase and zirconite phase.

[0058] In some embodiments, in the refractory material, the crystal phase includes 45-50% of mullite phase, 17-20% of corundum phase, 20-23% of baddeleyite phase and 10-13% of zirconite phase in terms of mass content.

[0059] In some embodiments, the thermal shock resistance of the fused zirconium mullite with a thickness of 65 mm, a length of 230 mm and a width of 114 mm is 30-50 times at 1100°C.

[0060] In some embodiments, the porosity of the fused zirconium mullite is 16-17.5%.

[0061] In some embodiments, the components in the electrically fused zirconia mullite satisfy the following conditions: mass fraction of Zr02> 32.5%, mass fraction of Al203> 42%, mass fraction of Si02≤ 18%, mass fraction of Ti02≤ 0.2%, mass fraction of Fe203≤ 0.2%, total mass fraction of Na20 and K20 ≤ 0.35%, and total mass fraction of CaO and MgO ≤ 0.35%. Further, in the electrically fused zirconia mullite, the mass fraction of Zr02is greater than 32.5% and less than 40%, the mass fraction of Al203is greater than 42% and less than 50%, the mass fraction of Si02is greater than 15% and less than or equal to 18%, the mass fraction of Ti02is greater than or equal to 0.1% and less than or equal to 0.2%, the mass fraction of Fe203is less than 0.2%, the total mass fraction of Na20 and K20 is greater than or equal to 0.1% and less than 0.35%, and the total mass fraction of CaO and MgO is greater than or equal to 0.1% and less than 0.35%.

[0062] In some embodiments, the components in the alumina powder satisfy the following conditions: mass fraction of Al203> 98.5%, mass fraction of Si02< 0.3%, mass fraction of Fe203≤ 0.1%, and total mass fraction of Na20 and K20 ≤ 0.35%. Further, in the alumina powder, the mass fraction of Al203is greater than 98.5% and less than 99.5%, the mass fraction of Si02is greater than 0.05% and less than 0.3%, the mass fraction of Fe203is greater than 0.02% and less than 0.1%, and the total mass fraction of Na20 and K20 is greater than 0.12% and less than 0.35%.

[0063] In some embodiments, the loss on ignition of the alumina powder is < 0.5%. Preferably, the loss on ignition of the alumina powder is 0.05% to 0.1%.

[0064] In some embodiments, the components in the zirconia powder satisfy the following conditions: mass fraction of Zr02> 65.5%, mass fraction of Si02< 34%, mass fraction of Fe203≤ 0.2%, and mass fraction of Ti02≤ 0.35%. Preferably, in the zirconia powder, the mass fraction of Zr02is greater than 90% and less than 99.9%, the mass fraction of Si02is less than 0.5%, the mass fraction of Fe203is greater than 0.01% and less than 0.1%, and the mass fraction of Ti02is greater than 0.1% and less than 0.35%.

[0065] In some embodiments, the electro-fused zirconia mullite comprises electro-fused zirconia mullite coarse material with a particle size greater than 3 mm and less than or equal to 5 mm, electro-fused zirconia mullite medium material with a particle size greater than 1.5 mm and less than or equal to 3 mm, electro-fused zirconia mullite fine material with a particle size greater than 0.5 mm and less than or equal to 1.5 mm, electro-fused zirconia mullite ultra-fine material with a particle size greater than 0.1 mm and less than or equal to 0.5 mm, and electro-fused zirconia mullite micro-powder with a D50 of 10 μm to 20 μm. The electro-fused zirconia mullite is added in different particle sizes, and the finer powder can fill the voids, so that the density of the refractory material is higher, and the porosity of the refractory material is reduced. The shrinkage of the refractory material can be further inhibited.

[0066] The D50 in the present application refers to the median particle size.

[0067] In some embodiments, the components in the electro-fused zirconia mullite coarse material, the electro-fused zirconia mullite medium material, the electro-fused zirconia mullite fine material, the electro-fused zirconia mullite ultra-fine material and the electro-fused zirconia mullite micro-powder can be the same or different, but all need to meet the component conditions of the electro-fused zirconia mullite described above.

[0068] In some embodiments, the D50 of the zirconia powder is 5 μm to 15 μm.

[0069] In some embodiments, the alumina powder comprises alumina powder A with a D50 of 1.5 μm to 2.5 μm and alumina powder B with a D50 of 3 μm to 6 μm.

[0070] In some embodiments, the raw material components comprise the following by mass fraction:

[0071] electro-fused zirconia mullite coarse material 10 parts to 35 parts,

[0072] electro-fused zirconia mullite medium material 5 parts to 25 parts,

[0073] electro-fused zirconia mullite fine material 3 parts to 15 parts,

[0074] electro-fused zirconia mullite ultra-fine material 15 parts to 25 parts,

[0075] electro-fused zirconia mullite micro-powder 5 parts to 10 parts,

[0076] alumina powder A 8 parts to 20 parts,

[0077] alumina powder B 2 parts to 10 parts,

[0078] zirconia powder 10 parts to 15 parts, and

[0079] water 5 parts to 7 parts.

[0080] As an example, the mass fraction of the electro-fused zirconia mullite coarse material can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or 35 parts. Further, the mass fraction of the electro-fused zirconia mullite coarse material can be a range value formed by any two point values above as end values. Preferably, the mass fraction of the electro-fused zirconia mullite coarse material is 20 parts to 30 parts. More preferably, the mass fraction of the electro-fused zirconia mullite coarse material is 25 parts to 30 parts.

[0081] As an example, the mass fraction of the electro-fused zirconia mullite medium material can be 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, or 25 parts. Further, the mass fraction of the electro-fused zirconia mullite medium material can be a range value formed by any two point values above as end values. Preferably, the mass fraction of the electro-fused zirconia mullite medium material is 8 parts to 17 parts. More preferably, the mass fraction of the electro-fused zirconia mullite medium material is 10 parts to 17 parts.

[0082] As an example, the mass fraction of the electro-fused zirconia mullite fine material can be 3 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, or 15 parts. Further, the mass fraction of the electro-fused zirconia mullite fine material can be a range value formed by any two point values above as end values. Preferably, the mass fraction of the electro-fused zirconia mullite fine material is 4 parts to 6 parts.

[0083] As an example, the mass fraction of the electro-fused zirconia mullite ultra-fine material can be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, or 25 parts. Further, the mass fraction of the electro-fused zirconia mullite ultra-fine material can be a range value formed by any two point values above as end values. Preferably, the mass fraction of the electro-fused zirconia mullite ultra-fine material is 19 parts to 21 parts.

[0084] As an example, the mass fraction of the electro-fused zirconia mullite micro-powder can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts. Further, the mass fraction of the electro-fused zirconia mullite micro-powder can be a range value formed by any two point values above as end values. Preferably, the mass fraction of the electro-fused zirconia mullite micro-powder can be 5 parts to 7 parts.

[0085] As an example, the mass fraction of the alumina powder A can be 8 parts, 10 parts, 11 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 19 parts, or 20 parts. Further, the mass fraction of the alumina powder A can be a range value formed by any two point values above as end values.

[0086] In some embodiments, the alumina powder A is composed of 40% to 60% of alumina powder A1 and 40% to 60% of alumina powder A2; wherein the D50 of the alumina powder A1 is 2 ± 0.1 μm; the D50 of the alumina powder A2 is 2.3 ± 0.1 μm. The components of the alumina powder A will be further controlled to be added in different median particle sizes, which is beneficial to the structure and sintering of the product.

[0087] In some embodiments, the refractory material includes 5-10 parts by mass of the alumina powder A1 and 5-10 parts by mass of the alumina powder A2.

[0088] For example, the mass fraction of the alumina powder B can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts. Further, the mass fraction of the alumina powder B can be a range value formed by any two point values as end values. Preferably, the mass fraction of the alumina powder B can be 3-5 parts.

[0089] It can be understood that the chemical components of the alumina powder A1, the alumina powder A2, and the alumina powder B can be the same or different, but all need to meet the above conditions.

[0090] For example, the mass fraction of the zirconia powder can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts. Further, the mass fraction of the zirconia powder can be a range value formed by any two point values as end values. Preferably, the mass fraction of the zirconia powder can be 12-14 parts.

[0091] In some embodiments, the preparation raw material of the refractory material further includes 0.2-0.4 parts by mass of a dispersion enhancer.

[0092] In some embodiments, the dispersion enhancer is inorganic clay. Using inorganic clay as a dispersion enhancer can make the body have better dispersibility and suspensibility, prevent particle sedimentation, and not affect the fluidity.

[0093] In some embodiments, the components in the inorganic clay meet the following conditions: the mass fraction of Al2O3 is <15%, the mass fraction of SiO2 is >50%, the mass fraction of CaO is ≤5%, and the mass fraction of MgO is ≤25%.

[0094] In some embodiments, the inorganic clay includes but is not limited to attapulgite.

[0095] In some embodiments, the D50 of the inorganic clay is 3-15 μm. Preferably, the D50 of the inorganic clay is 5-12 μm. More preferably, the D50 of the inorganic clay is 8-11 μm.

[0096] In some embodiments, the preparation raw material of the refractory material further includes 5-7 parts by mass of water. Adding water is beneficial to forming.

[0097] In some embodiments, the preparation raw material of the refractory material includes, by mass fraction:

[0098] electro-fused zircon mullite coarse aggregate 20-35 parts,

[0099] 25-35 parts of coarse fused zirconia mullite,

[0100] 4-6 parts of fine fused zirconia mullite,

[0101] 19-21 parts of super-fine fused zirconia mullite,

[0102] 5-7 parts of micro-fused zirconia mullite,

[0103] 5-10 parts of alumina powder A1,

[0104] 5-10 parts of alumina powder A2,

[0105] 3-5 parts of alumina powder B,

[0106] 12-14 parts of zirconia ball powder,

[0107] 0.2-0.4 parts of attapulgite, and

[0108] 5-7 parts of water.

[0109] In some embodiments, the raw materials for preparing the refractory material include, in parts by mass:

[0110] 25-35 parts of coarse fused zirconia mullite

[0111] 10-17 parts of medium fused zirconia mullite

[0112] 4-6 parts of fine fused zirconia mullite,

[0113] 19-21 parts of super-fine fused zirconia mullite,

[0114] 5-7 parts of micro-fused zirconia mullite,

[0115] 5-10 parts of alumina powder A1,

[0116] 5-10 parts of alumina powder A2,

[0117] 3-5 parts of alumina powder B,

[0118] 12-14 parts of zirconia ball powder,

[0119] 0.2-0.4 parts of attapulgite, and

[0120] 5.5-6.5 parts of water.

[0121] In another embodiment of the present application, a method for preparing a refractory material is provided. The method includes the following steps S10-S30.

[0122] S10, mixing the raw material components.

[0123] In some embodiments, the step of mixing the raw material components comprises:

[0124] First, the electro-fused zircon mullite, aluminum oxide powder, and zirconium oxide powder are mixed for 3-5 minutes. Then, water is added and wet mixing is performed for 4-7 minutes to obtain the mud.

[0125] S20, after mixing is completed, casting forming is performed to obtain the green body.

[0126] In some embodiments, the casting forming is vacuum casting forming. Through vacuum casting forming, the density and mechanical strength of the refractory material can be improved, and defects such as pores and inclusions can be reduced, further improving the corrosion resistance of the refractory material. In addition, the size and shape of the refractory material can be accurately controlled, improving the precision and consistency of the product.

[0127] In some embodiments, when vacuum casting forming is used, the vacuum degree is -0.08 MPa to -0.1 MPa.

[0128] In some embodiments, when vacuum casting forming is used, the forming pressure is 0.2 MPa to 0.4 MPa.

[0129] S30, calcining the green body to obtain the refractory material.

[0130] In some embodiments, the calcining temperature is 1300°C to 1500°C. As an example, the calcining temperature can be 1300°C, 1320°C, 1350°C, 1360°C, 1380°C, 1400°C, 1420°C, 1450°C, 1480°C, or 1500°C. Further, the calcining temperature can be a range value formed by any two of the above point values as end values. Preferably, the calcining temperature is 1380°C to 1420°C.

[0131] In some embodiments, the calcining time is 8h to 15h. As an example, the calcining time can be 8h, 9h, 10h, 11h, 12h, 13h, 14h, or 15h. Further, the calcining time can be a range value formed by any two of the above point values as end values. Preferably, the calcining time can be 9h to 11h.

[0132] In some embodiments, before the step of calcining the green body, a step of drying the green body is further included.

[0133] In some embodiments, the step of drying the green body comprises:

[0134] First, the green body is naturally dried for 120h to 240h, and then dried at 40°C to 80°C for 48h to 96h.

[0135] In yet another embodiment of the present application, there is provided an application of the above refractory material in preparing a refractory product. The refractory product includes but is not limited to a refractory brick.

[0136] The application scenarios of the refractory brick include but are not limited to a glass melting furnace, for example, can be used as a lip brick in a glass melting furnace.

[0137] In yet another embodiment of the present application, there is provided a refractory brick, the lip brick comprising the above refractory material.

[0138] In yet another embodiment of the present application, there is provided a glass melting furnace, the glass melting furnace comprising the above lip brick.

[0139] In order to make the purpose, technical scheme and advantages of the present application more concise and clear, the present application is described by the following specific examples, but the present application is not limited to these examples only. The examples described below are only better embodiments of the present application, which can be used to describe the present application, and cannot be understood as limiting the scope of the present application. It should be noted that any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

[0140] In order to better illustrate the present application, the content of the present application is further described below in combination with examples. The following are specific examples.

[0141] The information of each raw material used in each example and comparative example is as follows:

[0142] The electrofused zirconia mullite comprises the following components: the mass fraction of ZrO2 is 35-38%, the mass fraction of Al2O3 is 43-47%, the mass fraction of SiO2 is 16-18%, the mass fraction of TiO2 is 0.1-0.2%, the mass fraction of Fe2O3 is 0-0.2%, the total mass fraction of Na2O and K2O is 0.1-0.3%, and the total mass fraction of CaO and MgO is 0.1-0.3%. The product is purchased from Henan Changcheng Special High-temperature New Material Co., Ltd.

[0143] The electrofused zirconia mullite of the above components is crushed by a crusher, and then sieved by a screen to obtain electrofused zirconia mullite of different particle sizes as follows:

[0144] Electrofused zirconia mullite coarse material: greater than 3 mm and less than or equal to 5 mm;

[0145] Electrofused zirconia mullite medium material: greater than 1.5 mm and less than or equal to 3 mm;

[0146] Electrofused zirconia mullite fine material: greater than 0.5 mm and less than or equal to 1.5 mm;

[0147] Electro-fused zirconia mullite coarse powder: greater than 3 mm and less than or equal to 5 mm;

[0148] Electro-fused zirconia mullite fine powder: D50 = 10-20 μm.

[0149] Sintered zirconia mullite was purchased from Guangdong Xinlingnan Technology Co., Ltd. The sintered zirconia mullite of different particle sizes was obtained by crushing and sieving the sintered zirconia mullite of the same composition.

[0150] Sintered zirconia mullite coarse powder: greater than 3 mm and less than or equal to 5 mm;

[0151] Sintered zirconia mullite medium powder: greater than 1.5 mm and less than or equal to 3 mm;

[0152] Sintered zirconia mullite fine powder: greater than 0.5 mm and less than or equal to 1.5 mm;

[0153] Sintered zirconia mullite ultra-fine powder: greater than 0.1 mm and less than or equal to 0.5 mm.

[0154] The alumina powder includes the following components: the mass fraction of Al2O3 is 99.2%, the mass fraction of SiO2 is 0.24%, the mass fraction of Fe2O3 is 0.05%, and the total mass fraction of Na2O and K2O is 0.21%; the loss on ignition of the alumina powder is 0.07%.

[0155] The alumina powder of different particle sizes was obtained by crushing and sieving the alumina powder of the same composition.

[0156] Alumina powder A1: D50 = 2 μm.

[0157] Alumina powder A2: D50 = 2.3 μm.

[0158] Alumina powder B: D50 = 5.7 μm.

[0159] The zirconia powder includes the following components: the mass fraction of ZrO2 is 99.6%, the mass fraction of SiO2 is 0.12%, the mass fraction of Fe2O3 is 0.03%, and the mass fraction of TiO2 is 0.16%.

[0160] Zirconia powder: D50 = 8.4 μm.

[0161] Dispersed reinforcing agent: attapulgite, D50 = 10.2 μm, the chemical formula is (Mg, Al)5[(OH)2(Si, Al)8O 20 ]·8H2O, including the following components: the mass fraction of component SiO2 is 56.96% and the mass fraction of MgO is 23.83%. ​

[0162] Kaolin, D50 = 5.2 μm, product model is Maoming Nanshui brand kaolin N4.

[0163] Example 1

[0164] The preparation method of the refractory material of the present example is as follows:

[0165] 1. The raw materials were weighed according to the proportions of the raw material components shown in Table 1.

[0166] 2. The prepared electrically fused zircon mullite, alumina powder and zirconia powder were mixed in a mixer for 5 min; then the weighed water was added, and after wet mixing for 7 min, the mixture was discharged to obtain the mixed mud.

[0167] 3. The mud was placed in a vacuum machine, vacuumized, and then pressure cast into a mold. After the mold was filled, the casting was stopped. When the mud did not have a significant lower layer after about 30 minutes, the casting port was cut and flattened, and the mud was left to dry in place.

[0168] 4. After drying for 150 h, the dried material was placed in a drying oven at 70 °C and dried for another 48 h.

[0169] 5. The dried material was placed in a shuttle kiln for calcination, and the calcination temperature was controlled at 1400 °C, and the calcination time was 10 h.

[0170] Through XRD analysis, it was found that the crystal phase of the lip brick prepared in the present example included 45%~50% of mullite phase, 17%~20% of corundum phase, 20%~23% of zircon phase, and 10%~13% of zirconite phase.

[0171] Examples 2~4

[0172] Examples 2~4 used the same preparation method as Example 1, and the only difference was that the formula was different, as shown in Table 1.

[0173] Comparative Example 1

[0174] The preparation method of Comparative Example 1 was basically the same as that of Example 1, and the only difference was that the raw material component formula was different. Specifically, the raw material formula of each example and comparative example is shown in Table 1 below:

[0175] Table 1

[0176]

[0177] Performance test

[0178] Test method and result analysis

[0179] Apparent porosity: The apparent porosity of the refractory materials prepared in each example and comparative example was tested according to the method specified in standard GB / T 2997-2015.

[0180] Bulk density: The bulk density of the refractory materials prepared in each example and comparative example was tested according to the method specified in standard GB / T 2997-2015.

[0181] Compressive strength: The compressive strength of the refractory materials prepared in each example and comparative example was tested according to standard GB / T5072-2023.

[0182] Thermal shock resistance: The thermal shock resistance of the refractory materials prepared in each example and comparative example was tested according to standard DIN51068:2008-11.

[0183] Glass corrosion resistance test: In the glass corrosion resistance test experiment of the examples and comparative examples in the present application, the glass was Guangdong Chunjing bottle and jar white glass, the glass flow rate was 45 m / h, the size of the test bar was 15 mm x 15 mm x 108 mm, the experimental temperature and time were 1350℃ x 144h.

[0184] Foaming index: The foaming index of the examples and comparative examples in the present application was the ratio of the number of bubbles with a diameter >0.2 mm generated by the sample to the observed area (pieces / mm 2 ).

[0185] Crystal phase composition: The crystal phase composition of the refractory materials prepared in each example and comparative example was obtained by XRD equipment testing.

[0186] The test data of the apparent porosity, bulk density, thermal shock resistance, glass corrosion resistance, and foaming index of the refractory materials prepared in each example and comparative example are shown in Table 3.

[0187] The crystal phase composition of the refractory materials prepared in each example and comparative example is shown in Table 4.

[0188] Table 2

[0189]

[0190] From Table 2, it can be seen that the refractory materials prepared in Examples 1-4 have lower apparent porosity, higher bulk density, higher compressive strength, and better thermal shock resistance. In combination with Figure 1 , Figure 1 The surface effect diagram after foaming experiment of the refractory material prepared in Example 3. The refractory material prepared in Example 3 is basically free of bubbles with a diameter of more than 0.2 mm. Figure 1

[0191] ​Compared with example 1, different particle sizes of sintered zircon mullite material are used to replace different particle sizes of fused zircon mullite in comparative example 1. The refractory prepared in comparative example 1 has high apparent porosity, small bulk density, and poor compressive strength and thermal shock resistance compared with example 1. In combination with Figure 2 , Figure 2 The surface effect diagram of the refractory prepared in comparative example 1 after foaming experiment. It can be seen from Figure 2 that the refractory prepared in comparative example 1 contains more bubbles with a diameter of >0.3mm, and the foaming performance is not as good as that of example 1. Figure 3 a is the glass corrosion resistance diagram of the refractory brick prepared in comparative example 1, and b is the glass corrosion resistance diagram of the refractory brick prepared in example 1. In combination with table 2, the single direction erosion amount at 1 / 2 of the liquid level of the refractory prepared in comparative example 1 is 0.069mm / 24h, which is much larger than the single direction erosion amount at 1 / 2 of the liquid level of example 1 (0.041mm / 24h). It can be seen that the glass corrosion resistance of comparative example 1 is also not as good as that of example 1.

[0192] The technical features of the above-described examples can be combined in any way. In order to make the description simple, all possible combinations of the technical features in the above-described examples are not described, but as long as the combinations of the technical features do not contradict, they should be considered as the scope of the present disclosure.

[0193] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the present patent should be subject to the appended claims, and the description can be used to explain the content of the claims.

Claims

1. A refractory material, characterized in that, The raw materials for its preparation consist of the following components by mass: 55-80 parts of fused zircon mullite, 10-15 parts of zirconium oxide powder, 10-30 parts of alumina powder, 0.2-0.4 parts of dispersing reinforcing agent, and 5-7 parts of water; The refractory material contains crystalline phases, which, by mass content, include 45% to 50% mullite phase, 17% to 20% corundum phase, 20% to 23% zircon phase, and 10% to 13% zircon phase.

2. The refractory material as described in claim 1, characterized in that, The refractory material satisfies at least one of the following conditions: (1) The porosity of the electrofused zircon mullite is 16%~17.5%; (2) The components in the fused zircon mullite satisfy the following conditions: mass fraction of ZrO2 > 32.5%, mass fraction of Al2O3 > 42%, mass fraction of SiO2 ≤ 18%, mass fraction of TiO2 ≤ 0.2%, mass fraction of Fe2O3 ≤ 0.2%, total mass fraction of Na2O and K2O ≤ 0.35%, and total mass fraction of CaO and MgO ≤ 0.35%; (3) The components in the alumina powder meet the following conditions: the mass fraction of Al2O3 > 98.5%, the mass fraction of SiO2 < 0.3%, the mass fraction of Fe2O3 ≤ 0.1%, and the total mass fraction of Na2O and K2O ≤ 0.35%; the loss on ignition of the alumina powder < 0.5%; (4) The components in the zirconium oxide powder meet the following conditions: ZrO2 mass fraction > 65.5%, SiO2 mass fraction < 34%, Fe2O3 mass fraction ≤ 0.2%, and TiO2 mass fraction ≤ 0.35%.

3. The refractory material according to any one of claims 1 to 2, characterized in that, The refractory material satisfies at least one of the following conditions: (1) The fused zircon mullite includes coarse fused zircon mullite with a particle size greater than 3 mm and less than or equal to 5 mm, medium fused zircon mullite with a particle size greater than 1.5 mm and less than or equal to 3 mm, fine fused zircon mullite with a particle size greater than 0.5 mm and less than or equal to 1.5 mm, ultrafine fused zircon mullite with a particle size greater than 0.1 mm and less than or equal to 0.5 mm, and micro fused zircon mullite powder with a D50 of 10 μm to 20 μm; (2) The D50 of the zirconium oxide powder is 5μm~15μm; (3) The alumina powder includes alumina powder A with a D50 of 1.5μm to 2.5μm and alumina powder B with a D50 of 3μm to 6μm.

4. The refractory material as described in claim 3, characterized in that, By mass, the preparation materials include the following: The fused zircon mullite rough material is 10 to 35 parts. The fused zircon mullite aggregate consists of 5 to 25 parts. The fused zircon mullite fines consist of 3 to 15 parts. The fused zircon mullite ultrafine material is 15-25 parts. 5 to 10 parts of the fused zircon mullite micro powder The alumina powder A is 8 to 20 parts. The alumina powder B is 2 to 10 parts, and The zirconium oxide powder is 10 to 15 parts.

5. The refractory material as described in claim 3, characterized in that, Based on mass percentage, the alumina powder A is composed of 40%~60% alumina powder A1 and 40%~60% alumina powder A2; the D50 of the alumina powder A1 is 2μm±0.1μm; and the D50 of the alumina powder A2 is 2.3μm±0.1μm.

6. The refractory material according to any one of claims 1 to 2, characterized in that, The dispersing enhancer is inorganic clay; the inorganic clay satisfies at least one of the following conditions: (1) The chemical composition of the inorganic clay satisfies the following conditions: mass fraction of Al2O3 <15%, mass fraction of SiO2 >50%, mass fraction of CaO ≤5%, and mass fraction of MgO ≤25%; (2) The D50 of the inorganic clay is 3μm~15μm; (3) The inorganic clay includes at least one of attapulgite and kaolin.

7. The method for preparing the refractory material according to any one of claims 1 to 6, characterized in that, Includes the following steps: The raw materials are mixed and then cast into a mold to obtain a blank; The billet is calcined to obtain the refractory material.

8. The preparation method according to claim 7, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The casting process adopts vacuum casting; the vacuum degree of vacuum casting is -0.08MPa to -0.1MPa; the molding pressure is 0.2MPa to 0.4MPa; (2) Before calcining the billet, the process further includes a step of drying the billet; The drying steps include: first, air-drying the blank naturally for 120h~240h, and then drying it at 40℃~80℃ for 48h~96h; (3) The calcination temperature is 1300℃~1500℃; the calcination time is 8h~15h.

9. The use of the refractory material as described in any one of claims 1 to 6 in the preparation of refractory articles.

10. A refractory brick, characterized in that, It includes the refractory material as described in any one of claims 1 to 6.

11. A glass melting furnace, characterized in that, Including the refractory bricks as described in claim 10.

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