Refractory material and method of manufacture and use, heat treatment apparatus

Abstract

The application provides a refractory material and a preparation method and application thereof and a heat treatment device, wherein the first raw material for preparing the refractory material comprises, in percentage by mass, 23.5%-67.5% of fused zirconia, 10%-20% of zircon mullite, 0%-12% of zirconia, 19%-31% of a stabilizer, 3%-21% of a material containing an aluminum element and 0%-4.5% of an auxiliary agent; the fused zirconia comprises millimeter-level first fused zirconia and micron-level second fused zirconia; through the interaction formed by the specific raw material composition and proportion, the application solves the problem that the refractory material still maintains excellent compressive strength and thermal shock resistance while reducing the apparent porosity and improving the corrosion resistance and other performances, avoids the risk that the refractory material is cracked and cracked during the firing process, and further improves the general range of the refractory material, improves the use effect of the refractory material in a specific application scenario, and better improves the quality of the product.

Description

Technical Field

[0001] This application relates to the field of refractory materials technology, and in particular to refractory materials, their preparation methods and applications, and heat treatment apparatus. Background Technology

[0002] The core defects of traditional refractory materials lie in their insufficient high-temperature resistance, thermal shock resistance, erosion resistance, and unstable high-temperature physical properties. To meet the high demands of modern industry, new types of refractory materials have been developed, such as monolithic refractories, basic refractory bricks, and special ceramic refractories. Through process optimization or improvement, the overall performance of refractory materials has been enhanced to some extent. For example, high-zirconium bricks, which have seen relatively good improvements, are superior to traditional refractory bricks in terms of high-temperature resistance and erosion resistance, but still suffer from technical problems such as high apparent porosity, insufficient erosion resistance, compressive strength, and thermal shock resistance. Research shows that zirconium oxide can improve the structure of refractory materials, reducing apparent porosity while increasing density and erosion resistance. However, adding high amounts of zirconium oxide to refractory materials can easily lead to cracking and other defects during firing. Current technology still cannot balance the improvement of performance in zirconium-containing refractory materials with the stability and yield of the preparation process, making it difficult to control the quality of the finished product. Summary of the Invention

[0003] Therefore, it is necessary to provide a refractory material that can reduce the apparent porosity of the refractory material, improve its corrosion resistance, enhance its compressive strength and thermal shock resistance, improve the stability of the refractory material during the firing process, reduce the risk of cracking and fissures, and thus better improve and control the quality of the product.

[0004] In a first aspect, this application provides a refractory material, wherein the first raw material for preparing the refractory material, by mass percentage, comprises 23.5%-67.5% fused zirconium oxide, 10%-20% zirconium mullite, 0%-12% zirconium oxide, 19%-31% stabilizer, 3%-21% aluminum-containing material, and 0%-4.5% additives; the fused zirconium oxide comprises a first fused zirconium oxide and a second fused zirconium oxide, wherein the particle size of the first fused zirconium oxide is in the millimeter range, and the particle size of the second fused zirconium oxide is in the micrometer range.

[0005] In some embodiments, the first fused zirconia comprises fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 μm, the second fused zirconia comprises fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm and fused zirconia with a particle size of d < 2 μm; and / or, the mass ratio of the first fused zirconia to the second fused zirconia is (10-23):(22-38).

[0006] In some embodiments, the mass ratio of fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 mm, fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm, and fused zirconia with a particle size of d < 2 μm in the fused zirconia is (10 - 23) : (15 - 28) : (5 - 10); and / or, the first fused zirconia includes one or more of fused zirconia with a particle size of 2 mm ≤ d ≤ 3 mm, fused zirconia with a particle size of 1 mm < d < 2 mm, and fused zirconia with a particle size of 0.5 mm ≤ d ≤ 1 mm.

[0007] In some embodiments, the stabilizer includes one or more of yttrium-stabilized zirconia and calcium-stabilized zirconia; and / or, the aluminum-containing material includes alumina; and / or; the auxiliary agent includes one or more of a filler and an antioxidant.

[0008] In some embodiments, the alumina includes corundum; and / or, the particle size of the alumina is 3 μm ≤ d ≤ 0.5 mm; and / or, the filler includes kaolin; and / or; the antioxidant includes cerium oxide.

[0009] In some embodiments, preparing the refractory material further includes a second raw material, and the second raw material includes one or more of a binder, a reinforcing agent, a water reducing agent, and a solvent;

[0010] Optionally, the binder includes silica sol;

[0011] Optionally, the reinforcing agent includes attapulgite;

[0012] Optionally, the water reducing agent includes sodium hexametaphosphate;

[0013] Optionally, the solvent includes water;

[0014] Optionally, the mass ratio of the first raw material to the second raw material is 100 : (6 - 8).

[0015] In a second aspect, the present application further provides a method for preparing the refractory material provided in the first aspect, including the following steps:

[0016] Mix, pour, and solidify the first raw material for preparing the refractory material to form a green body;

[0017] After drying the green body, raise the temperature to the firing temperature at a heating rate of 5 °C / min - 25 °C / min for firing to prepare the refractory material;

[0018] Optionally, the second raw material can also be added during the mixing process.

[0019] In some embodiments, the drying temperature is 55°C-65°C; and / or the moisture content of the green body after drying is ≤0.5%; and / or the firing temperature is 1520°C-1580°C; and / or the firing time is 10h-12h.

[0020] Thirdly, this application also provides the application of a refractory material in the preparation of opalescent glass, wherein the refractory material includes the refractory material provided in the first aspect or the refractory material prepared by the preparation method provided in the second aspect.

[0021] Fourthly, this application also provides a heat treatment apparatus, wherein the lining of the heat treatment apparatus is prepared from the refractory material provided in the first aspect.

[0022] Compared with traditional technologies, the beneficial effects of the technical solution in this application include:

[0023] This application provides a refractory material. The first raw material for preparing the refractory material includes fused zirconia, zircon mullite, stabilizers, aluminum-containing materials, and additives in specific proportions. The fused zirconia comprises a first fused zirconia with a particle size in the millimeter range and a second fused zirconia with a particle size in the micrometer range. By selecting specific raw material components and controlling the addition ratio between them, this application achieves good interaction between the raw materials. Furthermore, by controlling the particle size of the fused zirconia, it achieves good flowability and filling effects in the system. This synergistically solves the problem of maintaining excellent compressive strength and thermal shock resistance while reducing apparent porosity and improving erosion resistance in refractory materials. It also prevents cracking and fissures during firing, thereby expanding the versatility of refractory materials, improving their performance in specific applications, and ultimately enhancing the quality of finished products. Detailed Implementation

[0024] To facilitate understanding of this application, preferred embodiments are provided below to provide a more complete description of the application. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to enable a thorough and complete understanding of the disclosure of this application.

[0025] 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 this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0026] As used herein, "optional," "optional," and "optional" refer to either "with" or "without" parallel options. If multiple "optional" entries appear in a technical solution, each "optional" entry is independent unless otherwise specified and there are no contradictions or mutual constraints. The term "and / or" as used herein includes any and all combinations of one or more related listed items. Unless otherwise specified, "multiple," "multiple," etc., as used herein refer to a quantity greater than 2 or equal to 2; for example, "one or more" indicates one, two, or more than two. In open-ended technical features or solutions described herein using words such as "containing," "including," and "comprising," unless otherwise specified, additional members beyond the listed members are not excluded. This can be considered as providing both a closed-ended feature or solution consisting of the listed members and an open-ended feature or solution that includes additional members beyond the listed members.

[0027] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0028] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0029] In this application, "particle size" refers to the equivalent particle size (or particle size distribution) of a homogeneous sphere (or combination) of a certain diameter when a certain physical property or behavior of the particle being tested is most similar to that of the particle. It should be understood that in this application, particles ≤0.1 mm can be within the D50 particle size range, and particles >0.1 mm refer to the particle size range measured by standard analytical sieves. However, the particle size testing scheme is not intended to limit this application; the technical effects of this application can be achieved within a reasonable particle size range. For ease of illustrating the particle size range, this application uses "d" to represent "particle size".

[0030] The "electrofused zirconia" involved in this application uses zircon sand as the main raw material and carbonaceous material as the reducing agent. In an electric arc furnace, the zircon sand is reduced and desilicated, and after spraying or casting, desilicated zirconia is produced. Among them, both electrofused high zircon particles and electrofused high zircon fine powder are electrofused zirconia, and the difference lies in the particle size. The "micrometer-scale" particle size in this application can be expressed as the particle size within the range of 0μm < d ≤ 999μm, preferably including the particle size within the range of 1μm ≤ d ≤ 10μm. The "millimeter-scale" particle size in this application can be expressed as the particle size within the range of 0mm < d ≤ 999mm, preferably including the particle size within the range of 0.5mm ≤ d ≤ 3mm.

[0031] The "stabilized zirconia" involved in this application refers to a material that inhibits the phase transformation of zirconia by doping substances including metals and metal oxides.

[0032] The "zircon mullite" involved in this application refers to mullite containing zirconia. The "electrofused zircon mullite" involved in this application refers to a material synthesized by a high-temperature electrofusion process with industrial alumina and zircon sand as the main raw materials.

[0033] The "corundum" involved in this application is a gem formed by the crystallization of alumina (Al2O3). Corundum doped with metal chromium is bright red in color and is generally called ruby, while blue or colorless corundum is generally classified into the category of sapphire. Among them, "electrofused corundum" is a material melted at high temperature in an electric arc furnace with industrial alumina or calcined alumina as the raw material. "Tabular corundum" is a pure sintered corundum that is fired and shrunk completely without adding any additives.

[0034] The "white corundum" involved in this application refers to a material refined with industrial alumina powder as the raw material using a modern new and unique process technology. Among them, "white corundum fine powder" is a powdery substance obtained by crushing, screening, and processing white corundum.

[0035] The "opal glass" involved in this application, also known as diffused glass, is made by injecting fluoride into transparent glass sintering, making the glass have good diffused transmission characteristics. It can be used to make cosine correction sheets and light source homogenizing sheets for various detectors, as well as opal glass bottles.

[0036] The lining materials of furnaces and kilns are typically high-temperature refractory materials. Due to the high internal temperature of the furnace, highly corrosive substances may be introduced or generated during product preparation, affecting the lining material and consequently the quality of the finished products. For example, fluorides contained in opaline glass can penetrate into the pores and gaps of the refractory material during preparation, damaging its structure and accelerating erosion. Furthermore, at high temperatures, these substances may react with the refractory material to form gases or volatiles, increasing porosity, reducing compressive strength and seismic resistance, and even causing cracks. Therefore, improving the performance of high-temperature refractory materials not only enhances the performance and extends the service life of the furnace but also allows for better control of product quality.

[0037] High-zirconia bricks are currently considered a type of high-temperature refractory material with relatively good performance improvements. Their main component, zirconium oxide, has a high content, which improves the structure and properties of high-temperature refractories to some extent, such as reducing apparent porosity and enhancing erosion resistance. However, due to the high zirconium oxide content, they cannot withstand high-temperature firing processes, leading to a tendency to crack during firing. Therefore, current high-zirconia bricks still cannot simultaneously satisfy the requirements of reducing apparent porosity, improving erosion and corrosion resistance, and ensuring good firing results without the risk of cracking or splitting.

[0038] Therefore, this application aims to reduce the apparent porosity of zirconium-containing refractory materials, improve their erosion resistance and other properties, while enhancing their compressive strength and thermal shock resistance, preventing cracking during the firing process, and better optimizing their performance and application scenarios.

[0039] In a first aspect, this application provides a refractory material, wherein, by mass percentage, the first raw material for preparing the refractory material comprises 23.5%-67.5% fused zirconium oxide, 10%-20% zirconium mullite, 0%-12% zirconium oxide, 19%-31% stabilizer, 3%-21% aluminum-containing material, and 0%-4.5% additives; the fused zirconium oxide comprises a first fused zirconium oxide and a second fused zirconium oxide, wherein the particle size of the first fused zirconium oxide is in the millimeter range, and the particle size of the second fused zirconium oxide is in the micrometer range.

[0040] This application uses specific amounts of fused zirconia, zirconium mullite, zirconium oxide, stabilizers, aluminum-containing materials, and additives as the first raw material for preparing refractory materials. These raw materials exhibit good compatibility and synergistic effects, collectively resolving the contradiction between structural improvement and firing stability in zirconium-containing refractories. Furthermore, by optimizing the addition amounts of each component in the raw materials, this application significantly reduces the apparent porosity of the refractory material, improves its structure, and enhances the chemical stability and corrosion resistance of the product. The specific raw material composition allows the zirconium-containing material to enter the glassy phase during firing, acting as its framework, thereby significantly improving the material's high-temperature compressive strength, thermal shock resistance, and refractoriness, thus enhancing its stability and service life and allowing for better quality control. In addition, through the rational selection and compounding of raw materials, this application produces high-quality products better suited for specific applications, such as reducing the corrosion of refractory materials by fluorides during the preparation of opalescent glass.

[0041] This application employs a mixture of granular (millimeter-scale) and micron-scale (micron-scale) fused zirconia. This optimizes the flowability of the raw materials and significantly improves the density and stability of the material. By matching granular and micron-scale fused zirconia, the problems of insufficient flowability and particle agglomeration caused by single-granular fused zirconia are addressed. At the same time, it reduces the porous structure formed between single-granular fused zirconia particles, which can lead to significant instability in the material, such as collapse and deformation. It also avoids the insufficient mechanical strength, cracking, severe corrosion, and poor thermal shock resistance caused by single-micron-scale fused zirconia.

[0042] In some preferred embodiments, the first raw material for preparing the refractory material, by weight percentage, includes 23.5%-67.5% fused zirconium oxide, 10%-20% zirconium mullite, 0%-12% zirconium oxide, 19%-31% stabilizer, 3%-21% aluminum-containing material, and 0.5%-4.5% additives; further, by weight percentage, the first raw material for preparing the refractory material includes 42%-55% fused zirconium oxide, 10%-20% zirconium mullite, 0%-12% zirconium oxide, 19%-31% stabilizer, 3%-21% aluminum-containing material, and 1%-4% additives.

[0043] In some preferred embodiments, the first raw material for preparing the refractory material, by weight percentage, comprises 45%-55% fused zirconium oxide, 12%-18% zirconium mullite, 0%-12% zirconium oxide, 22%-31% stabilizer, 3%-6% aluminum-containing material, and 1%-4% additives; further, by weight percentage, the first raw material for preparing the refractory material comprises 45%-55% fused zirconium oxide, 10%-15% zirconium mullite, 8%-12% zirconium oxide, 20%-25% stabilizer, 3%-6% aluminum-containing material, and 1%-4% additives.

[0044] In some embodiments, the first fused zirconia comprises fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 mm, and the second fused zirconia comprises fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm and fused zirconia with a particle size of d < 2 μm. This application, through extensive screening and optimization, has selected compositions of fused zirconia with particle sizes of 0.5 mm ≤ d ≤ 3 mm from millimeter-sized fused zirconia and 2 μm ≤ d ≤ 10 μm and d < 2 μm respectively from micrometer-sized fused zirconia. By matching multiple particle sizes of fused zirconia, the space-filling effect of fused zirconia is enhanced. The composite micro-powder of fused zirconia with multiple particle sizes can fill the pores between fused zirconia particles, improving the density and stability of the material, reducing the degree of material volume shrinkage, and minimizing phenomena such as material collapse and deformation. Through extensive experimentation, this application has optimized fused zirconia with particle sizes within a specific range and two micro-powder grades. The resulting refractory materials exhibit low apparent porosity, corrosion resistance, high compressive strength, and excellent thermal shock resistance.

[0045] This application achieves a good synergistic effect by mixing multiple micro-powder-grade fused zirconia in a particle-scale manner. By using a variety of micro-powder-grade fused zirconia with specific particle size ranges, a dense and stable refractory material is formed.

[0046] As a non-limiting example, fused zirconia with a particle size of d < 2 μm is selected from fused zirconia with a particle size of 1 μm ≤ d < 2 μm.

[0047] In some embodiments, the mass ratio of the first fused zirconia to the second fused zirconia is (10-23):(22-38); further, the mass ratio of the first fused zirconia to the second fused zirconia is (12-18):(30-35). The refractory material prepared has better erosion resistance and thermal shock resistance, and the prepared refractory material has low apparent porosity, high bulk density and excellent compressive strength.

[0048] In some embodiments, the mass ratio of fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 mm, fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm, and fused zirconia with a particle size of d < 2 μm in the fused zirconia is (10 - 23):(15 - 28):(5 - 10). By optimizing the compounding ratio of fused zirconia in three particle size ranges, it is found that the refractory material prepared from the fused zirconia composition formed within the ratio range has excellent effects. It can be seen that within the ratio range, the fused zirconia in the three particle size ranges can achieve mutual doping and filling, not only optimizing the fluidity and dispersibility of the preparation raw materials, but also forming a dense material. Further, the mass ratio of fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 mm, fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm, and fused zirconia with a particle size of d < 2 μm in the fused zirconia is (12 - 18):(25 - 28):(5 - 6).

[0049] In some embodiments, the first fused zirconia includes one or more of fused zirconia with a particle size of 2 mm ≤ d ≤ 3 mm, fused zirconia with a particle size of 1 mm < d < 2 mm, and fused zirconia with a particle size of 0.5 mm ≤ d ≤ 1 mm. Through optimization, it is found that selecting the fused zirconia within the above three millimeter-sized particle size ranges can form an ideal refractory material.

[0050] As a non-limiting example, the fused zirconia preferably has a zirconia content of ≥ 84%, and the refractory material prepared has better performance.

[0051] In some embodiments, the stabilizer includes one or more of yttrium-stabilized zirconia and calcium-stabilized zirconia. It should be understood that yttrium-stabilized zirconia or calcium-stabilized zirconia is a functional ceramic material that stabilizes the crystal structure of zirconia (ZrO2) by doping yttrium oxide (Y2O3) or calcium oxide (CaO), so that it also maintains a cubic crystal structure at room temperature. Its core advantage is to convert the monoclinic phase of zirconia itself, which is unstable at room temperature, into a cubic phase that is stable at room temperature.

[0052] In some embodiments, the material containing aluminum element includes alumina. As a non-limiting example, the particle size of alumina is 3 μm ≤ d ≤ 0.5 mm. As a non-limiting example, alumina includes corundum, and among them, corundum includes one or more of fused corundum and tabular corundum powder.

[0053] As a non-limiting example, alumina includes alumina micropowder, and the particle size of alumina micropowder is 3 μm - 3.5 μm.

[0054] As a non-limiting example, zirconium mordenite includes capacitance zirconium mordenite and / or sintered mordenite. Further, the zirconium mordenite is selected from capacitance zirconium mordenite, and the particle size of fused zirconium mordenite is 0.7 mm ≤ d ≤ 1.5 mm.

[0055] In some embodiments, the adjuvant includes one or more of a filler and an antioxidant. As a non-limiting example, the filler includes kaolin. As a non-limiting example, the antioxidant includes cerium oxide.

[0056] In some embodiments, the filler content is 0%-3.5%, including but not limited to 0%, 1%, 2%, 2.5%, 3%, 3.5%, or any range formed by both of the foregoing and values ​​within that range.

[0057] In some embodiments, the antioxidant content is 0.5%-1%, including but not limited to 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or any of the foregoing ranges and values ​​within those ranges.

[0058] In some preferred embodiments, the additives include fillers and antioxidants, and the amount of additives added is 0.5%-4.5% of the total weight percentage of the raw materials used to prepare the refractory material; further, the amount of additives added is 1%-4%.

[0059] In some embodiments, the raw materials for preparing the refractory material further include a second raw material, which includes one or more of a binder, a reinforcing agent, a water-reducing agent, and a solvent. As a non-limiting example, the binder includes silica sol. As a non-limiting example, the reinforcing agent includes attapulgite. As a non-limiting example, the water-reducing agent includes sodium hexametaphosphate. As a non-limiting example, the solvent includes water.

[0060] In some embodiments, the mass ratio of the first raw material to the second raw material is 100:(6-8).

[0061] In some embodiments, the second raw material includes a binder, a reinforcing agent, a water-reducing agent, and a solvent, wherein the mass ratio of the binder, the reinforcing agent, the water-reducing agent, and the solvent is (0.5-0.6):0.15:(0.01-0.05):(6.1-7).

[0062] Secondly, this application also provides a method for preparing the refractory material provided in the first aspect, comprising the following steps:

[0063] S10. The first raw material for preparing refractory materials is mixed, poured, and solidified to form a green body.

[0064] S20. After drying the green body, heat it to the firing temperature at a heating rate of 5℃ / min-25℃ / min to prepare refractory material.

[0065] Given the risk of cracking during the firing process of refractory materials, this application improves the raw materials for refractory materials and refines the preparation process for specific raw material compositions. Specifically, a specific heating program is used to control the temperature changes and thermal stress matching during the firing process, thereby balancing thermal expansion and contraction, reducing the generation and accumulation of internal stress, and preventing cracking during firing. The heating rate includes, but is not limited to, 5℃ / min, 10℃ / min, 15℃ / min, 20℃ / min, 25℃ / min, or any combination thereof and values ​​within that range. It is important to understand that the heating rate is controlled and optimized to match the raw material composition of the refractory material. Based on the specific composition of the raw materials used in this application, the sintering behavior and microstructure formation of the raw materials are controlled within the heating rate range to obtain a refractory material with excellent performance. If the heating rate is lower than 5℃ / min, although a relatively uniform internal crystal phase can be formed, the diffusion time in the low-temperature section is too long, which easily leads to surface pre-sintering, making it difficult for the internal pores in the high-temperature section to be discharged, resulting in insufficient compressive strength of the prepared refractory material. If the heating rate is higher than 25℃ / min, the internal stress of the material is uneven, resulting in obvious thermal stress defects. The prepared refractory material has high porosity, low density, and is prone to cracking.

[0066] Cracks during the firing process are mainly categorized into cracks in the preheating zone, firing zone, and cooling zone. Cracks in the firing and cooling zones are related to inconsistent shrinkage and phase transformation reactions, while cracks in the preheating zone are mostly caused by incomplete removal of residual moisture. Therefore, this application controls the residual moisture in the material by controlling the temperature during the drying process. In some embodiments, the drying temperature is 55℃-65℃, including but not limited to 55℃, 58℃, 60℃, 62℃, 65℃, or any combination thereof and values ​​within that range. Within this temperature range, residual moisture in the material is controlled, and the moisture content of the green body after drying is ≤0.5%, further reducing the risk of cracking during firing. Simultaneously, controlling the residual moisture content can also reduce the risk of the vapor pressure of residual moisture exceeding the higher original fracture strength of the refractory structure during firing, which could lead to explosive damage.

[0067] In some embodiments, the firing temperature is 1520°C-1580°C, including but not limited to 1520°C, 1540°C, 1560°C, 1580°C, or any combination thereof and values ​​within that range. Further, the firing temperature is 1520°C-1560°C.

[0068] In some embodiments, the firing time is 10h-12h, including but not limited to 10h, 10.5h, 11h, 11.5h, 12h or any of the foregoing ranges and values ​​within that range.

[0069] In some embodiments, the mixing process may further include adding a second raw material for mixing.

[0070] Thirdly, this application also provides an application of a refractory material in the preparation of opalescent glass, the refractory material including the refractory material provided in the first aspect. The refractory material prepared by this application has excellent mechanical strength, thermal shock resistance, and erosion resistance, and is particularly suitable for the firing of opalescent glass. It significantly improves the stability of the refractory material during the firing process of opalescent glass, reduces the erosion of the refractory material during the firing process of opalescent glass, improves the service stability and service life of the refractory material, and can also improve the quality of the product.

[0071] Fourthly, this application also provides a heat treatment apparatus, wherein the lining of the heat treatment apparatus is prepared from the refractory material provided in the first aspect.

[0072] In some embodiments, the heat treatment apparatus is used in the manufacturing process of an article, the article including glass, ceramics, etc., and the glass including opaline glass articles.

[0073] It should be noted that experimental methods in the following embodiments of this application, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All commonly used chemical reagents used in the embodiments are commercially available products, or can be prepared by those skilled in the art using known methods.

[0074] Example 1

[0075] This application provides a class of refractory materials, the raw material composition of which is shown in Table 1:

[0076] Table 1: Raw material composition of refractory materials (wt%)

[0077]

[0078] Note: " / " means no addition. The total mass of the first raw material is 100%. The mass fraction of the second raw material is calculated based on the mass of the main material, which is 100%.

[0079] The specific steps for preparing refractory materials are as follows:

[0080] Preparation of castable: The raw materials of each group of refractory materials in Table 1 are mixed in an inclined mixer for 8 minutes according to the formula ratio, and then wet-mixed for about 5 minutes before being discharged to form castable.

[0081] Vibration molding: Prepare the plaster mold and place it on the vibration table. After the vibration table is turned on, pour the casting material into the plaster mold at the same time. After pouring is full, stop pouring and observe the pouring gate. After no more air bubbles escape from the pouring gate, turn off the vibration and let it stand for 24 hours. After the casting material in the mold has initially solidified, remove the mold to form a green body.

[0082] Drying: The green billets are placed in a drying kiln at 60℃ and dried for 48 hours (ensuring that the core moisture content of the green billets does not exceed 0.5wt% of the total weight) before being loaded into the kiln.

[0083] Shuttle kiln loading and firing: The dried green body is placed on the base of the shuttle kiln, aligned with the longitudinal direction of the burner flame, avoiding direct contact with the burner flame. Then, the internal temperature of the shuttle kiln is raised to 1520℃-1560℃ at a heating rate of 10℃ / min and held for 11h±1h to form refractory material.

[0084] Comparative Example 1

[0085] This comparison provides a class of refractory materials, the raw material composition of which is shown in Table 2:

[0086] Table 2: Raw material composition of refractory materials (wt%)

[0087]

[0088] Note: " / " means no addition. The total mass of the first raw material is 100%. The mass fraction of the second raw material is calculated based on the mass of the main material, which is 100%.

[0089] The refractory material was prepared according to the raw material formulation provided in Table 2, following the preparation steps of Example 1.

[0090] Experimental Example 1

[0091] The refractory materials prepared from the raw materials in Tables 1 and 2 were subjected to performance tests. The test indicators included apparent state, apparent porosity, bulk density, compressive strength and resistance to water cooling and thermal shock. The specific test methods are shown in Table 3, and the test results are shown in Tables 4 and 5.

[0092] Table 3: Performance Testing Methods for Refractory Materials

[0093]

[0094] Table 4: Performance test results of the refractory material prepared in Example 1

[0095]

[0096] Table 5: Performance Test Results of Refractory Materials

[0097]

[0098] As shown in Tables 4 and 5, the refractory material provided in this application uses fused zirconium oxide, zirconium mullite, stabilizers, aluminum-containing materials, and additives as raw materials to achieve the preparation of refractory materials with low apparent porosity, high bulk density, excellent compressive strength, and excellent thermal shock resistance. Furthermore, the material maintains a good surface morphology even as the firing temperature increases, thereby further improving the material's performance.

[0099] Comparing the test results in Tables 4 and 5, it can be seen that the performance of the five groups of refractory materials in Table 5 is significantly lower than that of the group 1 in Table 4. Refractory materials numbered 1-2 and 1-5, fired at a temperature of 1520℃-1560℃, all exhibited cracking and network cracking. As the firing temperature increased, refractory materials numbered 1-3 and 1-4 also showed cracking and network cracking, indicating poor thermal shock resistance. While refractory material numbered 1-1 formed within this firing temperature range had a good surface, its apparent porosity was high, resulting in significantly insufficient compressive strength. In summary, this application demonstrates that by using fused zirconia, zircon mullite, stabilizers, aluminum-containing materials, and additives with specific particle sizes and contents, it is possible to prepare refractory materials with excellent comprehensive performance, and to improve the performance of the refractory materials by increasing the firing temperature.

[0100] Experimental Example 2

[0101] The refractory materials prepared from the raw materials in Example 1 and Comparative Example 1 (fired at 1560℃) were subjected to dynamic erosion resistance tests. The test method was dynamic resistance to glass melt erosion. The glass melt was milky white glass melt, the glass melt flow rate was 45 m / s, and it was kept at 1300℃ for 72 h. The test results are shown in Table 6.

[0102] Table 6: Results of dynamic erosion resistance of refractory materials

[0103]

[0104] As shown in Table 6, all 10 groups of refractory materials prepared in Example 1 of this application have excellent resistance to dynamic erosion, while the 5 groups of refractory materials prepared in Comparative Example 1 are more susceptible to erosion. This indicates that the refractory materials provided in this application can significantly improve the erosion resistance of refractory materials and resist the corrosion problems caused by firing during the preparation of opalescent glass products. They have good application effects in the preparation of opalescent glass.

[0105] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0106] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A refractory material, characterized in that, By mass percentage, the first raw materials for preparing the refractory material include 23.5%-67.5% of fused zirconia, 10%-20% of zircon mullite, 0%-12% of zirconia, 19%-31% of stabilizer, 3%-21% of aluminum-containing material, and 0%-4.5% of auxiliary agent; The fused zirconia includes first fused zirconia and second fused zirconia. The particle size of the first fused zirconia is in millimeters, and the particle size of the second fused zirconia is in micrometers.

2. The refractory material according to claim 1, characterized in that, The first fused zirconia includes fused zirconia with a particle size of 0.5mm ≤ d ≤ 3 mm, and the second fused zirconia includes fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm and fused zirconia with a particle size of d < 2 μm; and / or, the mass ratio of the first fused zirconia to the second fused zirconia is (10-23):(22-38).

3. The refractory material according to claim 2, characterized in that, The mass ratio of the fused zirconia with a particle size of 0.5 mm ≤ d ≤ 3 mm, the fused zirconia with a particle size of 2 μm ≤ d ≤ 10 μm, and the fused zirconia with a particle size of d < 2 μm in the fused zirconia is (10-23):(15-28):(5-10); and / or, the first fused zirconia includes one or more of fused zirconia with a particle size of 2mm ≤ d ≤ 3mm, fused zirconia with a particle size of 1mm < d < 2mm, and fused zirconia with a particle size of 0.5mm ≤ d ≤ 1mm.

4. The refractory material according to claim 1, characterized in that, The stabilizer includes one or more of yttria-stabilized zirconia and calcia-stabilized zirconia; and / or, the aluminum-containing material includes alumina; and / or; the auxiliary agent includes one or more of filler and antioxidant.

5. The refractory material according to claim 4, characterized in that, The alumina includes corundum; and / or, the particle size of the alumina is 3μm ≤ d ≤ 0.5mm; and / or, the filler includes kaolin; and / or; the antioxidant includes cerium oxide.

6. The refractory material according to any one of claims 1 to 5, characterized in that, Preparing the refractory material further includes a second raw material, and the second raw material includes one or more of binder, reinforcing agent, water reducing agent, and solvent; Optionally, the binder includes silica sol; Optionally, the reinforcing agent includes attapulgite; Optionally, the water reducing agent includes sodium hexametaphosphate; Optionally, the solvent includes water; Optionally, the mass ratio of the first raw material to the second raw material is 100:(6-8).

7. The method for preparing the refractory material according to any one of claims 1 to 6, characterized in that, Including the following steps: Mix, pour, and solidify the first raw materials for preparing the refractory material to form a green body; After drying the green body, heat it to the firing temperature at a heating rate of 5℃ / min - 25℃ / min for firing to prepare the refractory material; Optionally, the second raw material can also be added for mixing during the mixing process.

8. The method for preparing refractory materials according to claim 7, characterized in that, The temperature of the drying treatment is 55℃ - 65℃; and / or, the water content of the green body after drying treatment is ≤ 0.5%; and / or, the firing temperature is 1520℃ - 1580℃; and / or, the firing time is 10h - 12h.

9. The application of refractory materials in the preparation of opalescent glass, characterized in that, The refractory material includes the refractory material according to any one of claims 1 to 6 or the refractory material prepared by the preparation method according to claim 7 or 8.

10. A heat treatment apparatus, characterized in that, The lining in the heat treatment apparatus is prepared using the refractory material as described in any one of claims 1 to 6.

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