High-zirconium brick as well as preparation process and application thereof

Abstract

The invention discloses a high-zirconium brick as well as a preparation process and application thereof. The high-zirconium brick comprises the following components in percentage by weight: 40-99% of zirconium dioxide, 0.1-60% of aluminum oxide, and 0.1-40% of the sum of the weight of yttrium oxide, ferric oxide, titanium oxide, magnesium oxide, calcium oxide and silicon oxide. According to the method, heating and annealing cooling are controlled in a curve temperature control mode, all elements in the prepared high-zirconium brick are integrally uniform and free of segregation, the whole body density of the product is uniform and consistent, the defects of needle-shaped air holes, bubble retention, surface holes and the like do not exist, and the high-zirconium brick product prepared through the technological method is short in delivery cycle and can be produced in a customized mode.

Description

Technical Field

[0001] The present application relates to materials for glass furnaces, and specifically to a high-zirconia brick and its preparation process and application. Background Art

[0002] Materials for glass furnaces are generally divided into sintered materials and cast materials. Sintered materials, although their preparation process is relatively simple, are not suitable for the key parts in contact with the high-temperature glass liquid in glass furnaces because their porosity is generally high (about 10 - 30%), and problems such as bubbles and aggregate detachment are likely to occur when used in glass furnaces, resulting in defects such as bubbles and sand grains in glass products. In particular, for high-zirconia sintered materials added with stabilizers such as Y 2 O 3 , MgO, and CaO to avoid the monoclinic to tetragonal phase transformation of zirconia between 900°C and 1200°C, they have a large thermal expansion coefficient and are prone to thermal stress cracking during the heating process. At the same time, the stabilizers will dissolve in the glass liquid in the high-temperature environment of the glass furnace, resulting in the transformation of stabilized zirconia into an unstable state, and the phase transformation continues, making the material structure become fragile, which will also cause defects such as sand grains in the glass. Therefore, such materials are also not suitable for glass furnaces.

[0003] Relatively speaking, cast refractory materials are obtained by melting raw materials in an electric furnace, fully homogenizing them, pouring them into molds, and then cooling and solidifying. The products obtained have a dense structure and well-developed crystals, and are more suitable for the use environment of glass furnaces. Among them, cast materials with a high zirconia content are preferred materials in glass melting furnaces due to their excellent corrosion resistance. These materials are mainly divided into two categories: one is the Al 2 O 3 -ZrO 2 -SiO 2 series cast refractory materials with a zirconia content between 33% and 41%; the other is the high-zirconia content series cast refractory materials with a zirconia content as high as 80% to 95%. The latter has been widely used in high-quality glass furnaces in recent years due to its better corrosion resistance and low pollution to glass batch.

[0004] However, existing high-zirconia series refractory materials still have some defects. For example, due to the lower glass phase content compared to fused zirconia corundum (AZS) and the difference in cooling rate during the casting process, some materials will have an annual ring-like structure with a high porosity, which may lead to problems such as foaming. In addition, the large-scale application of high-zirconia series cast refractory materials is restricted due to low yield, long delivery cycle, and high price. At the same time, the large differences in application results are caused by factors such as poor thermal shock performance and low industry quality control ability of cast high-zirconia products. Therefore, the research and application of refractory materials for glass furnaces still need to be continuously explored and innovated to meet the needs of the glass industry for high-quality and high-performance refractory materials. Summary of the Invention

[0005] The purpose of this application is to provide a high-zirconia brick, its preparation process and application, so as to solve the problems of high manufacturing cost and poor thermal shock performance existing in the existing high-zirconia series of fused cast refractory materials.

[0006] To achieve the above purpose, this application provides the following technical solutions: In the first aspect, this application proposes a high-zirconia brick, and the high-zirconia brick includes the following components by weight percentage: zirconia 40% - 99%, alumina 0.1% - 60%, and the sum of the weights of yttrium oxide, iron oxide, titanium oxide, magnesium oxide, calcium oxide, and silicon oxide is 0.1% - 40%; Or the high-zirconia brick includes the following components by weight percentage: zirconia 40% - 99%, magnesium oxide 0.1% - 60%, and the sum of the weights of yttrium oxide, iron oxide, titanium oxide, calcium oxide, and silicon oxide is 0.1% - 40%; Or the high-zirconia brick includes the following components by weight percentage: zirconia 40% - 99%, calcium oxide 0.1% - 60%, and the sum of the weights of magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%; Or the high-zirconia brick includes the following components by weight percentage: zirconia 40% - 99%, chromium oxide 0.1% - 60%, and the sum of the weights of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%; Or the high-zirconia brick includes the following components by weight percentage: zirconia 40% - 99%, beryllium oxide 0.1% - 60%, and the sum of the weights of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%.

[0007] In the second aspect, this application proposes a preparation process of a high-zirconia brick, and the preparation process includes the following steps: Step 1: Weigh each component, mix them evenly, and react at 1800°C - 3000°C for at least 45 minutes to form a molten liquid or a solid-phase structure body, and cool to obtain a solid solution raw material; Step 2: Grind the solid solution raw material obtained in Step 1 into a powder with a D50 value of 0.2 - 100 microns; Step 3: Add 0.1% - 5% of an organic binder or an inorganic binder to the powder obtained in Step 2, and mix evenly; Step 4: Place the powder obtained in Step 3 in a mold, and press it into an initial blank at a pressure of not less than 500 tons for at least 15 seconds; Step 5: Heat the initial blank obtained in Step 4 from room temperature to 1600 - 1950°C by a temperature-controlled heating device in at least 5 hours, and keep it at not less than 1600°C for at least 1 hour, and then cool it to room temperature in at least 5 hours to obtain a high-zirconia brick blank; Step 6: Grind and trim the brick blank obtained in Step 5 to obtain a high-zirconia brick.

[0008] As a specific solution in the technical solution of the present application, the components after mixing in Step 1 are melted at least for 45 min at 1800°C to 3000°C and cooled to obtain a solid solution raw material with uniform element distribution; or the components after mixing are subjected to high-temperature liquid-phase reaction sintering at 1800°C to 3000°C for at least 60 min and cooled to obtain a solid solution raw material with uniform element distribution.

[0009] As a specific solution in the technical solution of the present application, the organic binder in Step 3 is selected from at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylamide (PAM), polyimide adhesive, epoxy adhesive, phenolic resin adhesive, and urea-formaldehyde resin adhesive; the inorganic binder includes but is not limited to paraffin and plant ash.

[0010] As a specific solution in the technical solution of the present application, the powder obtained in Step 3 is placed in a mold and formed by cold isostatic pressing with a pressure of 500 - 10000 tons or formed by a press under a pressure not less than 500 tons, and maintained for at least 15 seconds to obtain an initial blank. The mold includes but is not limited to rubber molds, polyurethane molds, and metal molds.

[0011] As a specific solution in the technical solution of the present application, the temperature control heating equipment in Step 5 uses a programmable temperature controller, sets the starting temperature as room temperature, the heating rate as 320 - 390°C / h, the heating time as at least 5 h, the end temperature as 1600 - 1950°C, and the holding time as at least 1 h.

[0012] As a specific solution in the technical solution of the present application, the temperature control heating equipment includes but is not limited to electric heating equipment, electromagnetic induction heating equipment, vacuum heating equipment, protective atmosphere heating equipment, gas heating equipment, plasma heating equipment, and microwave heating equipment.

[0013] As a specific solution in the technical solution of the present application, the cooling and annealing in Step 5 uses a programmable temperature controller, sets the starting temperature as the furnace temperature, the cooling rate as 390 - 320°C / h, the cooling time as at least 5 h, and the end temperature as room temperature.

[0014] In the third aspect, the present application proposes a high-zirconia brick for making various key ceramic products for glass furnaces, including but not limited to: crucibles for special glass, high-zirconia ceramic stirring paddles, high-zirconia ceramic bricks, high-zirconia wire-drawing crucibles, high-zirconia special-shaped fittings, and quartz furnaces.

[0015] Compared with the prior art, the beneficial effects of this application are as follows: According to the requirements of different glass melt varieties and compositions, reasonable raw materials for each component are selected to improve the best service life and cost performance of high-zirconium brick products. Moreover, this application innovates the preparation process route of high-zirconium bricks. By using a programmable temperature controller to control heating and annealing cooling in a curve temperature control mode, the elements in the prepared high-zirconium bricks are overall uniform without segregation, the density of the whole product is uniform, and there are no defects such as acicular pores, bubble retention, and surface holes, and there is no risk of local erosion and leakage of materials. The high-zirconium brick products prepared by the process method of this application have a short delivery cycle and can be customized for production. Under high-temperature conditions, the liquid-phase solidification structure is stable, the bubble precipitation rate is extremely low, the erosion resistance is strong, the thermal shock resistance is excellent, and the thermal penetration temperature decreasing performance is good, ensuring the safety of the kiln baking process. Especially in a long-term working environment above 1550 °C, compared with fused AZS and fused 95 products, it has more obvious advantages. Moreover, during customized production, the cost can be controlled by controlling the composition according to the actual needs of customers to match different customer requirements for cost performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is the process flow chart of the high-zirconium brick preparation proposed in the embodiment of this application; Figure 2 It is the microscope image of the high-zirconium brick sample proposed in the embodiment of this application; Figure 3 It is the thermal shock and thermal penetration practice diagram of the high-zirconium brick sample proposed in the embodiment of this application; Figure 4 It is the linear expansion rate test report of the high-zirconium brick sample proposed in the embodiment of this application; Figure 5 It is the 1300 °C bubble precipitation rate test report of the high-zirconium brick sample proposed in the embodiment of this application; Figure 6 It is the 1500 °C bubble precipitation rate test report of the high-zirconium brick sample proposed in the embodiment of this application; Figure 7 It is the erosion resistance test result diagram of the crucible made of the high-zirconium brick sample, the 41# zirconia corundum brick crucible and the 95# fused high-zirconium brick proposed in the embodiment of this application DETAILED DESCRIPTION OF THE EMBODIMENTS

[0017] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be further described clearly and completely below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] In order to solve the defects existing in the high zirconia series refractory materials proposed in the background art, the preparation process of the high zircon brick product is innovated in this embodiment. Moreover, according to the varieties and compositions of different glass melts, multiple component compositions of the high zircon brick are provided, aiming to improve the best service life and cost performance of the high zircon brick product. For example, this application proposes that the high zircon brick includes the following components by weight percentage: zirconia 40% - 99%, alumina 0.1% - 60%, and the sum of the weights of yttrium oxide, iron oxide, titanium oxide, magnesium oxide, calcium oxide, and silicon oxide is 0.1% - 40%; or the high zircon brick includes the following components by weight percentage: zirconia 40% - 99%, magnesium oxide 0.1% - 60%, and the sum of the weights of yttrium oxide, iron oxide, titanium oxide, calcium oxide, and silicon oxide is 0.1% - 40%; or the high zircon brick includes the following components by weight percentage: zirconia 40% - 99%, calcium oxide 0.1% - 60%, and the sum of the weights of magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%; or the high zircon brick includes the following components by weight percentage: zirconia 40% - 99%, chromium oxide 0.1% - 60%, and the sum of the weights of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%; or the high zircon brick includes the following components by weight percentage: zirconia 40% - 99%, beryllium oxide 0.1% - 60%, and the sum of the weights of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide is 0.1% - 40%. In order to avoid defects such as element segregation, inability to remove pores and bubbles, uneven density, and surface microcracks in the high zircon brick product caused by the casting process, this application improves the preparation process of the high zircon brick. First, the components after uniform mixing react at 1800 - 3000°C for at least 45 minutes to form a molten liquid or solid-phase structure body, and after cooling, a solid solution raw material with uniform distribution is obtained. Specifically, the components after mixing are melted at 1800°C - 3000°C for at least 45 minutes, and after cooling, a solid solution raw material with uniform element distribution is obtained; or the components after mixing are subjected to high-temperature liquid-phase reaction sintering at 1800°C - 3000°C for at least 60 minutes, and after cooling, a solid solution raw material with uniform element distribution is obtained; then the obtained solid solution raw material is ground into a powder with a D50 value of 0.2 - 100 microns; then 0.1% - 5% of an organic binder or an inorganic binder is added and mixed evenly; then in a mold, it is pressed into an initial blank under a pressure of not less than 500 tons for at least 15 seconds; the initial blank is heated from room temperature to 1600 - 1950°C by a temperature-controlled heating device in at least 5 hours, and is maintained at not less than 1600°C for at least 1 hour, and then cooled to room temperature in at least 5 hours to obtain a high zircon brick blank; after grinding and trimming, a high zircon brick product is manufactured.

[0019] In the specific implementation process of this application, the organic binder is selected from at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylamide (PAM), polyimide adhesive, epoxy adhesive, phenolic resin adhesive, and urea-formaldehyde resin adhesive; the inorganic binder includes but is not limited to paraffin and plant ash. The powder after adding the binder is placed in a mold and formed by cold isostatic pressing with a pressure of 500 - 10,000 tons or formed by a press under a pressure of not less than 500 tons, and maintained for at least 15 seconds to obtain an initial green body. The mold includes various types, but is not limited to rubber molds, polyurethane molds, and metal molds. The temperature control heating equipment uses a programmable temperature controller, with the starting temperature set at room temperature, the heating rate at 320 - 390 °C / h, the heating time at least 5 h, the end temperature at 1600 - 1950 °C, and the holding time at least 1 h. For cooling and annealing, the programmable temperature controller is used, with the starting temperature set at the furnace temperature, the cooling rate at 390 - 320 °C / h, the cooling time at least 5 h, and the end temperature at room temperature. The temperature control heating equipment includes but is not limited to electric heating equipment, electromagnetic induction heating equipment, vacuum heating equipment, protective atmosphere heating equipment, gas heating equipment, plasma heating equipment, and microwave heating equipment. In the specific implementation process, the temperature control heating equipment uses a curve temperature control method to heat and cool and anneal the initial green body of the high zirconia brick, control the growth of zirconia grains and anneal, and the prepared high zirconia brick product has uniform elements without segregation, uniform density throughout, no defects such as needle-shaped pores, air bubbles remaining, and surface holes, and no local erosion and leakage phenomena. Therefore, the high zirconia brick product prepared by the process method of this application has a short delivery cycle and can be customized for production. The high zirconia brick prepared by this application is used to make various key ceramic products for glass furnaces, including but not limited to: crucibles for special glass, high zirconia ceramic stirring paddles, high zirconia ceramic bricks, high zirconia wire drawing crucibles, high zirconia special-shaped fittings, and quartz furnaces. Example

[0021] In this example, the following raw material components with mass ratios are selected: 77% zirconia, 17% alumina, and the sum of the weights of yttrium oxide, titanium oxide, calcium oxide, magnesium oxide, and silicon oxide is 5%, among which the weight of silicon oxide is 0.4%, and the weights of titanium oxide and calcium oxide are both 0.1%.

[0022] Step 1: With a total mass of 5000 g, weigh each component in proportion, mix them evenly, keep them melted at 1900 °C for 60 min, and then cool to obtain a solid solution raw material with uniform element distribution; Step 2: Grind the solid solution raw material with uniform element distribution obtained in Step 1 into a powder with a D50 value of 0.2 - 20 microns; Step 3: Add 3% of polyvinyl alcohol (PVA) organic binder to the powder obtained in Step 2, and then mix them evenly; Step 4: Place the powder obtained in Step 3 in a metal mold and cold isostatically press it at a pressure of 600 tons for 20 seconds to obtain an initial blank. Step 5: Put the initial blank obtained in Step 4 into the curve temperature controller of the electromagnetic induction heating equipment. Heat it from room temperature to 1950°C at a rate of 320°C / h within 5 hours, and then keep the temperature at 1950°C for 2 hours. Then, cool it from 1950°C to room temperature at a rate of 320°C / h within 6 hours to obtain a high zirconia brick blank. Step 6: Grind and trim the brick blank obtained in Step 5 to obtain a high zirconia brick sample.

[0023] Element distribution detection of high zirconia brick samples Entrust the high zirconia brick sample prepared in Example 1 to a professional German testing institution to detect its element distribution. As Figure 2 is the microscopic image of the high zirconia brick sample. It can be clearly seen in the area indicated by the white arrow. These areas show a dense and highly dispersed particle distribution. These particles are mainly zirconia (ZrO 2 ), ZrO 2 particles are cleverly embedded in the matrix material, forming a tight and stable combination, ensuring the stable existence of ZrO 2 particles in the matrix, effectively avoiding the problem of the destabilization rate of the stable phase. It not only enhances the overall strength and toughness of the high zirconia brick but also broadens the application prospect of the monoclinic zirconia crystal form.

[0024] Thermal shock and thermal penetration practice and testing Use the box-type high-temperature furnace FM1800 equipment to conduct thermal shock and thermal penetration tests on the high zirconia brick prepared in Example 1. First, trim the size of the high zirconia brick to a length of 320 mm, a width of 310 mm, and a thickness of 70 mm. Then, heat one side of the high zirconia brick to 1600°C at a rate of 40°C / h within 40 hours. After that, keep the high zirconia brick at 1600°C for 4 hours, with the other side exposed to room temperature. Test the temperature of the other side exposed to room temperature to evaluate its thermal shock performance and thermal penetration performance. As Figure 3 shown. The following Table 1 shows the temperature change of the other side exposed to room temperature detected during the heating process of one side of the high zirconia brick and whether cracks appear on the surface.

[0025] Table 1 Temperature change statistical table In this experiment, the thermal shock process was from room temperature of 29 degrees to 1600 degrees, taking 40 hours, with a 4-hour heat preservation. During the heating process, there were no visible abnormal changes on the inner and outer surfaces of the high-zirconia bricks, and no cracks occurred. When the high temperature in the furnace reached 1600 °C, the temperature detected on the other side of the high-zirconia brick exposed to the air was 600 °C, with a thermal penetration temperature difference of 1000 °C, and the temperature decreased by 14 °C per 1 mm. It has excellent thermal shock resistance and good performance in the decreasing of thermal penetration temperature.

[0026] Linear expansion rate test The high-zirconia brick sample prepared in Example 1 was entrusted to the National Quality Inspection and Testing Center for Refractories for linear expansion rate detection. As Figure 4 shown in the test report, the linear expansion rate of the high-zirconia brick was in a continuous rising process from 0.02% to 0.38% from 50 to 600 °C, in a continuous decreasing process from 0.36% to 0.22% from 650 to 1000 °C, and was 0.73% at 1400 °C; under the same conditions, the linear expansion rate of the fused AZS 41# from 100 to 1000 °C was an increasing 4.23 - 0.81%; from the comparison data of the high-zirconia brick and the fused AZS 41# in Table 2 below, the linear expansion rate of the high-zirconia brick at the service temperature was almost the same as that of the AZS41#, but the probability of cracks occurring during the preheating process and the thermal shock process was relatively low, ensuring the safety of the kiln baking process.

[0027] Table 2 Comparison of linear expansion data Bubble precipitation test The high-zirconia brick sample prepared in Example 1 was entrusted to the National Quality Supervision and Inspection and Testing Center for Refractories Products of the Building Materials Industry for bubble precipitation test. As Figures 5 - 6 shown in the test report, it can be seen from the test report that the bubble precipitation rate of the high-zirconia brick was 0 at 1300 °C and 0.1 at 1500 °C; Table 3 shows the comparison data of the bubble precipitation rates of the high-zirconia brick, AZS41 and fused 95. From the analysis of the data over the years by the national inspection center, the bubble precipitation rate of the fused AZS was 1 - 1.2 (different differences were caused by the sampling parts of element segregation, and it gradually increased in the later stage due to the factor of glass phase seepage during long-term use); the bubble precipitation rate of the fused 95 high-zirconia was 26.50 (excessive release was caused by the volatilization of carbon retention in the early stage and would gradually decrease in the later stage); from the comparison data, the high-zirconia brick had a good inhibition of bubble defects caused to the glass furnace materials. Because its elements and density were uniform and there were no factors of phase structure change, its bubble precipitation data was always extremely low and remained stable. High zircon brick sample Cast ASZ41# Cast 95 1300℃ 0 1~1.2 26.5 1500℃ 0.1 Not measured Not measured

[0028] Table 3 Comparison data of bubble precipitation rates Erosion resistance test In this test, a crucible made of the high-zirconia brick sample prepared in Example 1 was used to conduct a comparative experiment on erosion resistance with a 41# zirconia corundum brick crucible and a 95# cast high-zirconia brick crucible. High-lead glass (erosion medium) was added to the crucible, and the test method was the static crucible method. The experimental temperature was 1600 °C and the heat preservation time was 36 h. From Figure 7 c It can be seen that silicon oxide precipitated inside the 41# zirconia corundum brick crucible, and the brick surface and crucible holes were all penetrated by the glass into the interior, causing honeycomb holes; Figure 7 b There was an approximately 1 mm hole expansion at the liquid level of the 95# cast high-zirconia brick, and there was a color change with a depth of approximately 5 mm into the brick material. Moreover, the remaining glass was turbid in color, and there might be a situation of component replacement; for the crucible made of the high-zirconia brick sample prepared in Example 1, there was an approximately 0.5 mm hole expansion at the liquid level of the high-zirconia brick (as Figure 7 a), there was no obvious color change at the position in contact with the high-lead glass, and the glass was relatively transparent, indicating that the high-zirconia brick prepared through this example had excellent erosion resistance.

[0029] Although the embodiments of the present application have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principle and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high zirconium brick, characterized in that: The high zirconium brick comprises the following components by weight percentage: 40% to 99% zirconium dioxide, 0.1% to 60% aluminum oxide, and 0.1% to 40% by weight of yttrium oxide, iron oxide, titanium oxide, magnesium oxide, calcium oxide, and silicon oxide; Or the high zirconium brick comprises the following components by weight percentage: 40% to 99% zirconium dioxide, 0.1% to 60% magnesium oxide, and 0.1% to 40% by weight of yttrium oxide, iron oxide, titanium oxide, calcium oxide, and silicon oxide; Or the high zirconium brick comprises the following components by weight percentage: 40% to 99% zirconium dioxide, 0.1% to 60% calcium oxide, and 0.1% to 40% by weight of magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide; Or the high zirconium brick comprises the following components by weight percentage: 40% to 99% zirconium dioxide, 0.1% to 60% chromium oxide, and 0.1% to 40% by weight of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide; Or the high zirconium brick comprises the following components by weight percentage: 40% to 99% zirconium dioxide, 0.1% to 60% beryllium oxide, and 0.1% to 40% by weight of calcium oxide, magnesium oxide, yttrium oxide, iron oxide, titanium oxide, and silicon oxide.

2. A process for preparing high zirconium bricks as claimed in claim 1, characterized in that: The preparation process comprises the following steps: Step 1, weigh each component, mix them evenly, react at 1800°C to 3000°C for at least 45 minutes to form a molten liquid or solid phase structure, and cool to obtain a solid solution raw material; Step 2: Grind the solid solution raw material obtained in step 1 into a powder with a D50 value of 0.2 to 100 microns; Step 3: Add 0.1-5% organic binder or inorganic binder to the powder obtained in step 2 and mix well; Step 4: placing the powder obtained in step 3 in a mold, and pressing and molding at a pressure of not less than 500 tons for at least 15 seconds to obtain an initial embryo; Step 5: Heat the initial body obtained in step 4 from room temperature to 1600-1950°C by a temperature control heating device within at least 5 hours, and keep it at not less than 1600°C for at least 1 hour, and then cool it to room temperature within at least 5 hours to obtain a high zirconium brick body; Step 6: Grind and trim the brick body obtained in step 5 to obtain high-zirconium bricks.

3. The preparation process according to claim 2, characterized in that: In the step 1, the mixed components are melted at 1800°C-3000°C for at least 45 minutes and cooled to obtain a solid solution raw material with uniformly distributed elements; or the mixed components are sintered at a high temperature of 1800°C-3000°C by liquid phase reaction for at least 60 minutes and cooled to obtain a solid solution raw material with uniformly distributed elements.

4. The preparation process according to claim 2, characterized in that: In the step three, the organic binder is selected from at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylamide (PAM), polyimide adhesive, epoxy adhesive, phenolic resin adhesive, and urea-formaldehyde resin adhesive; the inorganic binder includes but is not limited to paraffin wax and wood ash.

5. The preparation process according to claim 2, characterized in that: The powder obtained in step 3 is placed in a mold, and is formed by cold isostatic pressing at a pressure of 500-10,000 tons or by a press machine at a pressure of not less than 500 tons, and is maintained for at least 15 seconds to obtain an initial embryo body.

6. The preparation process according to claim 2, characterized in that: The molds include but are not limited to rubber molds, polyurethane molds, and metal molds.

7. The preparation process according to claim 2, characterized in that: In the step 5, the temperature control and heating equipment adopts a programmable temperature controller, and the starting temperature is set to room temperature, the heating rate is 320-390°C / h, the heating time is at least 5h, the end temperature is 1600-1950°C, and the insulation time is at least 1h.

8. The preparation process according to claim 7, characterized in that: Temperature control heating equipment includes but is not limited to electric heating equipment, electromagnetic induction heating equipment, vacuum heating equipment, protective atmosphere heating equipment, gas heating equipment, plasma heating equipment, and microwave heating equipment.

9. The preparation process according to claim 2, characterized in that: The cooling annealing in step 5 adopts a programmable temperature controller, sets the starting temperature to the furnace temperature, the cooling rate to 390-320° C. / h, the cooling time to at least 5 hours, and the end temperature to room temperature.

10. A high zirconium brick as claimed in any one of claim 1 is used to make various key ceramic products for glass kilns, including but not limited to: crucibles for special glass, high zirconium ceramic stirring paddles, high zirconium ceramic bricks, high zirconium drawing crucibles, high zirconium special-shaped accessories, and quartz furnaces.

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