Chromium-zirconium-corundum aggregate and preparation method thereof, chromium-zirconium-corundum composite material and preparation method and application thereof

Abstract

The present application relates to a chrome-zirconium-corundum aggregate and a preparation method thereof, a chrome-zirconium-corundum composite material and a preparation method and application thereof. The chrome-zirconium-corundum aggregate provided in the present application is based on a reasonable proportion of the weight proportions of each component and selects four types of granules with different particle sizes, which can enhance the coordination between the particles, so that when it is used to prepare corundum bricks for glass kilns, it can significantly reduce the apparent porosity of the corundum bricks and improve the compressive strength of the chrome-zirconium-corundum composite material. Furthermore, the chrome-zirconium-corundum aggregate provided in the present application also has the advantages of high volume density and excellent high-temperature performance, so that the volume density, load softening temperature and thermal shock resistance of the chrome-zirconium-corundum composite material can be improved, and the service life of the glass kiln can be extended.

Description

Technical Field

[0001] The present application relates to the technical field of refractory material preparation, and in particular to a chromium-zirconium-corundum aggregate and a preparation method thereof, a chromium-zirconium-corundum composite material and a preparation method and application thereof. Background Art

[0002] Glass is an essential material for human production and life. It needs to be prepared at high temperatures (maximum temperature can reach 1600℃ or higher), so refractory materials are required for glass kilns. In order to increase the life of the kiln and increase corrosion resistance, chrome-zirconium corundum bricks are used as refractory materials.

[0003] Chrome-zirconium corundum bricks are subjected to high temperature, physical and chemical erosion of glass liquid and mechanical scouring for a long time in the melting furnace. The degree to which chrome-zirconium corundum bricks can withstand these effects determines the life of the glass furnace. Under high temperature environment, chrome-zirconium corundum bricks will be affected by thermal expansion and thermal stress, which can easily lead to cracking, peeling or deformation of corundum bricks during thermal cycles; under the physical and chemical erosion and mechanical scouring of glass liquid, the wear of the brick body will accelerate, shortening the service life of the corundum brick. Therefore, in order to increase the service life of corundum bricks, it is necessary to reduce the apparent porosity of corundum bricks and improve the compressive strength of the material to reduce the impact of high temperature environment, physical and chemical erosion of glass liquid and mechanical erosion on corundum bricks. However, the poor coordination between the particles in traditional chrome-zirconium corundum bricks leads to an increase in the apparent porosity of the bricks and a decrease in the compressive strength. Summary of the invention

[0004] Based on this, the present application provides a chromium-zirconium-corundum aggregate and a preparation method thereof, a chromium-zirconium-corundum composite material and a preparation method and application thereof. The chromium-zirconium-corundum aggregate provided in the present application is used to prepare corundum bricks for glass kilns, which can significantly reduce the apparent porosity of the corundum bricks and improve the compressive strength of the corundum bricks.

[0005] In a first aspect of the present application, a chromium-zirconium-corundum aggregate is provided, comprising the following components in parts by weight:

[0006]

[0007] In parts by weight, the chemical composition of the first pellet, the second pellet, the third pellet and the fourth pellet includes 15 to 60 parts of Cr 2 O 3 , 9 to 12 parts of ZrO 2 , 25 to 39 parts of Al 2 O 3 , 8 to 12 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 .

[0008] The second aspect of the present application provides a method for preparing the chromium-zirconium corundum aggregate described in the first aspect of the present application, comprising the following steps:

[0009] Prepare raw materials according to the chemical composition of the first pellet, the second pellet, the third pellet and the fourth pellet,

[0010] The raw materials are wet ball-milled to prepare aggregate slurry;

[0011] The aggregate slurry is subjected to filter pressing and vacuum slurry kneading, and then extruded into aggregate mud strips;

[0012] The aggregate mud strips are dried and then calcined at a high temperature of 1560° C. to 1700° C., and then crushed to prepare the first granular material, the second granular material, the third granular material and the fourth granular material.

[0013] In a third aspect of the present application, a chromium-zirconium-corundum composite material is provided, comprising the following components in parts by weight:

[0014]

[0015] In one embodiment, the mixed matrix powder comprises the following components in parts by weight:

[0016]

[0017] In one embodiment, the mixed matrix powder has one or more of the following characteristics:

[0018] (1) In terms of weight, the chemical composition of the chromium powder includes 71 to 80 parts of Cr 2 O 3 , 5 to 10 parts of ZrO 2 , 2 to 8 parts of Al 2 O 3 , 2 to 10 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 ;

[0019] (2) In parts by weight, the Al-containing 2 O 3 The chemical composition of the powder includes 96 to 99 parts of Al 2 O 3 And 0 to 0.2 parts of Fe 2 O 3 ;

[0020] (3) In terms of weight, the chemical composition of the zircon powder includes 62 to 65 parts of ZrO 2, 32 to 35 parts of SiO 2 , 0.2 to 0.5 parts of Al 2 O 3 and 0.05 to 0.3 parts of Fe 2 O 3 .

[0021] In one embodiment, the chromium-zirconium-corundum composite material has one or more of the following features:

[0022] (1) The dispersant is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate;

[0023] (2) The thickening suspending agent is selected from one or more of sodium benzoate and attapulgite.

[0024] In a fourth aspect of the present application, there is provided a method for preparing the chromium-zirconium-corundum composite material according to any one of the embodiments of the third aspect of the present application, comprising the following steps:

[0025] Take the chromium-zirconium-corundum aggregate and the mixed matrix powder described in the first aspect of the present application according to weight proportions to prepare a mixed material;

[0026] After dry mixing the mixed material, the dispersant, the thickening suspending agent and the solvent are added and mixed to prepare a wet material;

[0027] The wet material is subjected to vacuum casting to prepare a molding blank;

[0028] The chromium-zirconium-corundum composite material is prepared by drying and firing the molded blank.

[0029] In one embodiment, the process parameters of vacuum casting include: vacuum degree ≤-0.08MPa.

[0030] In one embodiment, the preparation method has one or more of the following characteristics:

[0031] (1) The process parameters of the blank drying include: drying temperature of 40°C to 110°C, drying time ≥ 24h;

[0032] (2) The firing process parameters include: heating the temperature to 1540°C to 1630°C at a heating rate of 5°C / h to 15°C / h, and keeping the temperature for 8h to 16h.

[0033] In a fifth aspect of the present application, a corundum brick for a glass kiln is provided, comprising the chromium-zirconium-corundum composite material described in any one of the embodiments of the third aspect of the present application.

[0034] The chromium-zirconium-corundum aggregate provided in the present application is based on a reasonable ratio of the weight proportions of each component and selects four types of particles with different particle sizes, which can enhance the coordination effect between the particles. Therefore, when it is used to prepare corundum bricks for glass kilns, it can significantly reduce the apparent porosity of the corundum bricks and improve the compressive strength of the chromium-zirconium-corundum composite material.

[0035] Furthermore, the chromium-zirconium-corundum aggregate provided in the present application also has the advantages of high volume density and excellent high-temperature performance, thereby being able to improve the volume density, load softening temperature and thermal shock resistance of the chromium-zirconium-corundum composite material, and extend the service life of the glass kiln. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 to Figure 3 This is a morphology diagram of the chromium-zirconium-corundum composite material prepared in Example 1 of the present application;

[0037] Figure 4 This is the XRD diagram of the chromium-zirconium-corundum composite material prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0038] The following is a further complete and clear description of the chromium-zirconium-corundum aggregate and its preparation method, the chromium-zirconium-corundum composite material and its preparation method and application of the present application in combination with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0040] As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.

[0041] In this application, "first aspect", "second aspect", "third aspect", "fourth aspect", "fifth aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", "fifth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0042] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0043] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0044] The percentage contents involved in this application, unless otherwise specified, refer to mass percentage for solid-liquid mixing and solid-solid mixing, and refer to volume percentage for liquid-liquid mixing.

[0045] The percentage concentrations mentioned in this application, unless otherwise specified, refer to the final concentration, which refers to the percentage of the added component in the system after the addition of the component.

[0046] The temperature parameters in this application, unless otherwise specified, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range of instrument control.

[0047] In a first aspect of the present application, a chromium-zirconium-corundum aggregate is provided, comprising the following components in parts by weight:

[0048]

[0049] In parts by weight, the first pellet, the second pellet, the third pellet and the fourth pellet include 15 to 60 parts of Cr 2 O 3 , 9 to 12 parts of ZrO 2 , 25 to 39 parts of Al 2 O 3 , 8 to 12 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 .

[0050] It can be understood that the first granule of the present application includes granules with a particle size of any value between 4 mm and 6 mm, and any granule with a particle size between 4 mm and 6 mm can be used as the first granule. Accordingly, granules with a particle size of any value between 2 mm ≤ particle size < 4 mm can be used as the second granule. Granules with a particle size of any value between 0.5 mm ≤ particle size < 2 mm can be used as the third granule. Granules with a particle size < 0.5 mm can be used as the fourth granule.

[0051] The weight proportions of the first granule include, but are not limited to, 10, 12, 15, 18 or 20 parts. The weight proportions of the second granule include, but are not limited to, 10, 12, 15, 16 or 18 parts. The weight proportions of the third granule include, but are not limited to, 10, 12, 15, 16 or 18 parts. The weight proportions of the fourth granule include, but are not limited to, 20, 21, 25, 26, 27 or 28 parts.

[0052] The components of the first pellet, the second pellet, the third pellet and the fourth pellet include 15 to 60 parts of Cr 2 O 3 , 9 to 12 parts of ZrO 2 , 25 to 39 parts of Al 2 O 3 , 8 to 12 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 It should be noted that the composition of the first pellet, the second pellet, the third pellet and the fourth pellet can be independently selected from 15 to 60 parts of Cr 2 O 3 , 9 to 12 parts of ZrO 2 , 25 to 39 parts of Al 2 O 3 , 8 to 12 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 Specifically, Cr 2 O 3 The weight parts include but are not limited to 15 parts, 17 parts, 18 parts, 19 parts, 20 parts, 30 parts, 40 parts, 50 parts or 60 parts. 2 O 3 The weight parts include but are not limited to 25 parts, 30 parts, 35 parts, 38 parts or 39 parts. SiO 2 The weight parts of Fe include but are not limited to 8 parts, 10 parts or 12 parts. 2 O 3 The weight parts include but are not limited to 0.2 parts, 0.3 parts, 0.4 parts or 0.5 parts.

[0053] The chrome-zirconium-corundum aggregate provided by the present application is based on a reasonable proportion of the weight fractions of each component, and four different particle sizes of particles are selected, which can enhance the coordination between the particles, so that when it is used to prepare corundum bricks for glass kilns, the apparent porosity of the corundum bricks can be significantly reduced, and the compressive strength of the chrome-zirconium-corundum composite material can be improved. Furthermore, the chrome-zirconium-corundum aggregate provided by the present application also has the advantages of high volume density and excellent high-temperature performance, so that the volume density, load softening temperature and thermal shock resistance of the chrome-zirconium-corundum composite material can be improved, and the service life of the glass kiln can be extended.

[0054] The second aspect of the present application provides a method for preparing the chromium-zirconium corundum aggregate described in the first aspect of the present application, comprising the following steps:

[0055] Prepare raw materials according to the composition of the first pellet, the second pellet, the third pellet and the fourth pellet,

[0056] The raw materials are wet ball-milled to prepare aggregate slurry;

[0057] The aggregate slurry is subjected to filter pressing and vacuum slurry kneading, and then extruded into aggregate mud strips;

[0058] The aggregate mud strips are dried and then calcined at a high temperature of 1560° C. to 1700° C., and then crushed to prepare the first granular material, the second granular material, the third granular material and the fourth granular material.

[0059] In one example, raw materials for preparing the first granular material, the second granular material, the third granular material and the fourth granular material include zircon sand, chromium oxide green and aluminum oxide powder.

[0060] In one example, the particle size of the aggregate slurry is 2 μm to 5 μm. In the present application, the particle size of the aggregate refers to the size of the aggregate particles used.

[0061] In one example, the zircon powder includes 62 to 65 parts by weight of ZrO 2 , 32 to 35 parts of SiO 2 , 0.2 to 0.5 parts of Al 2 O 3 and 0.05 to 0.3 parts of Fe 2 O 3 .

[0062] In one example, the wet ball milling time is 3 h to 5 h.

[0063] In a third aspect of the present application, a chromium-zirconium-corundum composite material is provided, comprising the following components in parts by weight:

[0064]

[0065] It is understandable that the weight portion of the chromium zirconium corundum aggregate can be selected from any value between 50 and 74 parts. Specifically, the weight portion of the chromium zirconium corundum aggregate includes but is not limited to 50, 55, 60, 70 or 74 parts. The weight portion of the mixed matrix powder includes but is not limited to 35, 37, 39, 40 or 42 parts. The weight portion of the dispersant includes but is not limited to 0.05, 0.08, 0.1, 0.15, 0.18 or 2 parts. The weight portion of the thickening suspending agent includes but is not limited to 0.1, 0.15, 0.2, 0.25 or 0.3 parts.

[0066] In order to increase the compatibility of each component, a solvent needs to be added to the raw material, and the solvent is 5 to 8 parts by weight. It can be understood that the weight of the solvent includes but is not limited to 5 parts, 6 parts, 7 parts or 8 parts. In one example, the solvent includes one or more of water, water glass and silica sol.

[0067] The chromium-zirconium-corundum composite material provided in the present application uses chromium-zirconium-corundum aggregate as the main material, fully utilizing the advantages of good compatibility between the particles thereof, large bulk density and excellent high-temperature performance thereof, and further adding mixed matrix powder, dispersant and thickening suspending agent for filling, assisted by a firing process, thereby forming an aluminum-chromium solid solution mixture with uniform phase distribution, thereby being able to reduce the apparent porosity of the chromium-zirconium-corundum composite material, increase the bulk density, improve the compressive strength, improve the load softening temperature and enhance the thermal shock resistance.

[0068] In one example, the mixed matrix powder includes the following components in parts by weight:

[0069]

[0070] It is understood that the particle size of the chromium powder includes but is not limited to 44 μm, 40 μm, 35 μm, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm or 5 μm. Preferably, the particle size of the chromium powder is 20 μm to 44 μm. 2 O 3 The particle size of the powder includes but is not limited to 5 μm, 4 μm, 3 μm, 2 μm or 1 μm. 2 O 3 The particle size of the powder is 2.5 μm to 5 μm. The particle size of the zircon powder includes but is not limited to 2.5 μm, 2 μm, 1.5 μm, 1 μm or 0.5 μm. Preferably, the particle size of the zircon powder is 0.5 μm to 2.5 μm.

[0071] In the mixed matrix powder, the weight proportion of the chromium powder includes but is not limited to 22 parts, 25 parts or 28 parts. 2 O 3 The weight proportions of the powder include, but are not limited to, 5, 8, 10, 15 or 18. The weight proportions of zircon powder include, but are not limited to, 3, 4, 5 or 6. The weight proportions of kaolin include, but are not limited to, 1, 2, 2.5 or 3.

[0072] By rationally proportioning the components in the mixed matrix powder, it can have excellent compatibility with the chrome-zirconium-corundum aggregate, so as to further cooperate with the chrome-zirconium-corundum aggregate to improve the density of the chrome-zirconium-corundum composite material.

[0073] In one example, the chromium powder includes 71 to 80 parts by weight of Cr 2 O 3 , 5 to 10 parts of ZrO 2 , 2 to 8 parts of Al 2 O 3 , 2 to 10 parts of SiO 2 And 0.2 to 0.5 parts of Fe 2 O 3 .

[0074] In one example, the Al-containing 2 O 3 The powder includes 96 to 99 parts of Al 2 O 3 And 0 to 0.2 parts of Fe 2 O 3 .

[0075] In this application, it is not limited to 2 O 3 Powder type, containing Al 2 O 3 The types of powders include but are not limited to sintered tabular corundum, fused white corundum and calcined α-Al 2 O 3 .

[0076] In one example, the zircon powder includes 62 to 65 parts by weight of ZrO 2 , 32 to 35 parts of SiO 2 , 0.2 to 0.5 parts of Al 2 O 3 and 0.05 to 0.3 parts of Fe 2 O 3 .

[0077] In one example, the dispersant is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate.

[0078] In one example, the thickening suspending agent is selected from one or more of sodium benzoate and attapulgite. Attapulgite is a crystalline hydrated magnesium aluminum silicate mineral, which is earthy and dense in block form and is produced in sedimentary rocks and weathering crusts. It is white, off-white, blue-gray, gray-green or has a weak silky luster. The soil is fine, has an oily luster, is light, brittle, has a shell-like or jagged fracture, and has strong water absorption. It is sticky and plastic when wet, shrinks little after drying, and does not crack.

[0079] It is understandable that the present application does not limit the type of attapulgite, and common attapulgite A type and attapulgite Y type can be used as thickening suspending agents. Attapulgite A type is a mixture of cellulose-like materials (such as coconut palm fiber, straw, etc.) and clay particles. Attapulgite Y type is a composite material composed of clay, inorganic gelling materials and fillers (such as sand, gravel, etc.). Adding a thickening suspending agent in the present application can form a certain concave-convex structure in the composite material, thereby improving the durability and compressive strength of the composite material.

[0080] In one specific example, the chromium-zirconium-corundum composite material includes the following components in parts by weight:

[0081]

[0082]

[0083] In one specific example, the chromium-zirconium-corundum composite material includes the following chemical components in parts by weight:

[0084]

[0085] At present, chrome-zirconium corundum bricks are mainly prepared by electric melting and pressing and sintering. The chrome-zirconium corundum bricks produced by electric melting have the problem of high cost and are difficult for manufacturers to accept. Pressing and sintering methods include isostatic pressing and casting. Among them, isostatic pressing equipment is expensive, and dry powder needs to be manually filled in during the molding process, which will cause dust pollution, high labor intensity, low production efficiency, and short service life of rubber molds, which need to be replaced frequently, affecting efficiency.

[0086] Casting refractory materials are widely used in high-temperature fields due to their simple preparation process, high production efficiency, energy saving, low cost, and convenient construction. However, traditional casting refractory materials contain a lot of binders, which are difficult to dry; there is a lot of binder removal during the sintering process, the density of the green body after sintering is low, and there are easy spots on the surface during mechanical processing, and the surface roughness is high.

[0087] Although vacuum casting of refractory materials can further reduce the pores of the castables, these pores are difficult to completely eliminate in a vacuum environment. As a result, the prepared materials may have a high porosity or micropores, which affect the density and performance of the materials, so that metal ions and impurities in the glass liquid can easily penetrate into the refractory materials through the pores, destroying the material structure and seriously reducing the service life of the refractory materials.

[0088] In a fourth aspect of the present application, there is provided a method for preparing the chromium-zirconium-corundum composite material as described in any example of the third aspect of the present application, comprising the following steps:

[0089] Take the chromium-zirconium-corundum aggregate and the mixed matrix powder described in the first aspect of the present application according to weight proportions to prepare a mixed material;

[0090] After dry mixing the mixed material, the dispersant, the thickening suspending agent and the solvent are added and mixed to prepare a wet material;

[0091] The wet material is subjected to vacuum casting to prepare a molding blank;

[0092] The chromium-zirconium-corundum composite material is prepared by drying and firing the molded blank.

[0093] In one example, the process parameters of vacuum casting include: vacuum degree ≤-0.08MPa. In the present application, the vacuum degree includes but is not limited to -0.08MPa or -0.1MPa. The chromium zirconium corundum aggregate provided in the present application can enhance the coordination between the particles, and therefore can be effectively applied to the steps of vacuum casting and molding, and with the coordination of the mixed matrix powder, dispersant and thickening suspending agent, the compactness of the material can be significantly improved, thereby effectively preventing the metal ions and impurities in the glass liquid from penetrating into the interior of the refractory material through the pores, further improving the service life of the refractory material.

[0094] In one example, the process parameters for drying the molded blank include: a drying temperature of 40° C. to 110° C., and a drying time of ≥ 24 hours.

[0095] In one example, the firing process parameters include: heating to 1540°C to 1630°C at a heating rate of 5°C / h to 15°C / h, and keeping the temperature for 8h to 16h. It can be understood that the holding temperature for firing includes but is not limited to 1540°C, 1550°C, 1560°C, 1600°C, 1610°C, 1620°C or 1630°C.

[0096] In one specific example, the preparation method of the chromium-zirconium-corundum composite material comprises the following steps:

[0097] S1. Mix zircon sand, chromium oxide green, and aluminum oxide powder according to weight, add appropriate amount of water and mix in a stirring ball mill for 3h to 5h to make aggregate slurry with a particle size of 2μm to 5μm, filter press, vacuum mud, and squeeze into aggregate mud strips, air-dry and dry the aggregate mud strips, then calcine at 1560℃ to 1700℃, and finally crush into the first pellet, the second pellet, the third pellet, and the fourth pellet;

[0098] S2. Select chromium powder with a particle size of ≤44μm and Al-containing powder with a particle size of ≤5μm according to the weight ratio. 2 O 3 powder, zircon powder with a particle size of ≤2.5 μm and kaolin to prepare a mixed matrix powder;

[0099] S3. Select the first pellet, the second pellet, the third pellet and the fourth pellet in step S1 according to the weight ratio, and put the mixed matrix powder in step S2 into a medium-speed mixer and dry mix for 3min to 5min to prepare a mixed material;

[0100] S4. Add dispersant and water to the mixed material in step S3, wet mix for 1min to 3min, then add thickening suspending agent, stir for 6min to 15min until the surface turns slurry, and prepare wet material;

[0101] S5. The wet material of step S4 is injected into a vacuum mixer, evacuated for 5min to 15min until the vacuum degree is ≤-0.08MPa, and then injected into a plaster mold through a vacuum tube, and naturally dried for 24 to 48h, and then demolded and dried to prepare a molded blank;

[0102] S6. Place the formed blank of step S5 in a drying kiln for drying at a temperature of 40 to 110°C for a drying time of ≥24 hours; fire the dried product, and during the firing process, heat it to 1540-1630°C at a heating rate of 5 to 15°C / h and keep it warm for 8 to 16 hours to prepare a chromium-zirconium-corundum composite material.

[0103] In a fifth aspect of the present application, a corundum brick for a glass kiln is provided, comprising the chromium-zirconium-corundum composite material described in any example of the third aspect of the present application.

[0104] The following are specific examples. Unless otherwise specified, the raw materials used in the examples are all commercially available products.

[0105] Example 1

[0106] Example 1 of the present application provides a chromium-zirconium-corundum composite material, which includes the following components in parts by weight:

[0107]

[0108] The preparation method of the chromium-zirconium-corundum composite material in Example 1 of the present application is as follows: S1. Select zircon sand, industrial chromium oxide green, and industrial alumina powder, and mix them evenly according to the weight proportions, then add 5 to 8 parts of water and mix and grind in a stirring ball mill for 5 hours to make an aggregate slurry with a particle size requirement of 2 to 5 μm, and then filter and vacuum slurry, extrude into aggregate mud strips, air-dry and dry the aggregate mud strips, and then calcine at 1700°C, and finally crush them into the first, second, third, and fourth particles. S2. Mix the chromium powder, Al-containing 2 O 3 S3. Take the first pellet, the second pellet, the third pellet, the fourth pellet, the chromium powder after pulverization, the Al-containing powder after pulverization, and the zircon powder according to the weight proportions. 2 O 3 The powder and the crushed zircon powder are placed in a medium-speed mixer, dry mixed for 5 minutes, then dispersant NP3 and water are added, mixed for 3 minutes, and then attapulgite is added. After strong stirring for 15 minutes until the surface is slurried, the material is injected into a vacuum mixer, vacuumed for 15 minutes until the vacuum degree is -0.08MPa, and then injected into a gypsum mold through a vacuum tube. After natural drying for 48 hours, demolding and drying are obtained to obtain a blank. S5. The blank prepared in S4 is placed in a drying kiln for drying at a drying temperature of 110°C and a drying time of 24 hours; the dried product is fired at a firing temperature of 1630°C, a heat preservation time of 16 hours, and a heating rate of 15°C / h to obtain a chromium-zirconium-corundum composite material.

[0109] Example 2

[0110] Example 2 of the present application provides a chromium-zirconium-corundum composite material, which includes the following components in parts by weight:

[0111] In parts by weight, it includes the following components:

[0112]

[0113] Example 3

[0114] Example 3 of the present application provides a chromium-zirconium-corundum composite material, which includes the following components in parts by weight:

[0115] In parts by weight, it includes the following components:

[0116]

[0117]

[0118] Example 4

[0119] Example 4 of the present application provides a chromium-zirconium-corundum composite material, which includes the following components in parts by weight:

[0120] In parts by weight, it includes the following components:

[0121]

[0122] Example 5

[0123] Example 5 of the present application provides a chromium-zirconium-corundum composite material, which includes the following components in parts by weight:

[0124] In parts by weight, it includes the following components:

[0125]

[0126] Example 6

[0127] Example 6 is basically the same as Example 1, with the main difference being that attapulgite type A is not added in Example 4.

[0128] Example 7

[0129] Example 7 is basically the same as Example 1, with the main difference being that in Example 5, the weight portion of the chromium powder is 20 parts, the weight portion of kaolin is 5 parts, and the weight portion of attapulgite is 0.1 parts.

[0130] Example 8

[0131] Example 8 is basically the same as Example 1, with the main difference being that the weight portion of the chromium powder is 25 parts, and no kaolin is added.

[0132] Comparative Example 1

[0133] Comparative Example 1 is basically the same as Example 1, with the main difference that the fourth pellet with a particle size of less than 0.5 mm is not included in Comparative Example 1. Specifically, the weight portion of the first pellet is 18 parts, the weight portion of the second pellet is 22 parts, and the weight portion of the third pellet is 25 parts.

[0134] Comparative Example 2

[0135] Comparative Example 2 is basically the same as Example 1, with the main difference being that the content of aggregate in Comparative Example 2 is different from that in Example 1, specifically, the weight portion of the first aggregate is 5 parts, the weight portion of the second aggregate is 20 parts, the weight portion of the third aggregate is 22 parts, and the weight portion of the fourth aggregate is 18 parts.

[0136] The weight percentages of the raw material components in the chromium-zirconium-corundum composite materials of the present application examples and comparative examples are shown in Table 1. The main components of the chromium-zirconium-corundum composite materials in Table 1 are: the first pellet, the second pellet, the third pellet, the fourth pellet, the chromium powder, the Al-containing 2 O 3The total weight of the powder, zircon powder and kaolin is 100 parts, and the weight parts of the dispersant, suspension thickener and solvent are proportioned according to the main components of the chromium-zirconium-corundum composite material.

[0137] Table 1

[0138]

[0139]

[0140] The apparent porosity and volume density of the chromium-zirconium-corundum composite materials of the examples and comparative examples of the present application are measured based on the standard GB / T2997-2015, the compressive strength is measured based on the standard GB / T 5072-2008 (method 1), the load softening temperature is measured based on the standard GB / T5989-2008, and the thermal shock resistance is tested based on the standard DIN51068:2008-11. The test results are shown in Table 2.

[0141] Table 2

[0142]

[0143] As can be seen from Table 1, the chromium-zirconium-corundum composite material provided in the embodiments of the present application has lower apparent porosity, lower bulk density, higher compressive strength, higher softening temperature under load and higher thermal shock resistance. In Comparative Example 1, the fourth aggregate was not added, so that the apparent porosity of the composite material increased and the bulk density decreased, and its compressive strength and thermal shock resistance were both poor. Comparative Example 2 changed the composition of the components in the aggregate, which resulted in a larger apparent porosity, lower bulk density and compressive strength, and poor thermal shock resistance. In Example 6, attapulgite was not added, and its apparent porosity was slightly larger, which resulted in slightly poorer compressive strength and thermal shock resistance. In Example 7, the weight portion of kaolin was slightly more, resulting in slightly lower compressive strength, softening temperature under load and thermal shock resistance. In Example 8, kaolin was not added, and its apparent porosity was slightly larger, which resulted in slightly poorer compressive strength.

[0144] Depend on Figure 1 to Figure 4 It can be seen that the chromium-zirconium-corundum composite material prepared in Example 1 of the present application has large and uniform grains and few open pores, forming a structurally stable aluminum-chromium solid solution, wherein the presence of baddeleyite and zircon phases can improve the thermal shock resistance of the chromium-zirconium-corundum composite material, thereby improving the high-temperature performance of the corundum refractory material.

[0145] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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.

[0146] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A chromium-zirconium-corundum composite material, characterized in that: The composition comprises the following components by weight: 50 to 74 parts of chromium-zirconium-corundum aggregate, 35 to 42 parts of mixed matrix powder, 0.05 to 0.2 parts of dispersant, and 0.1 to 0.3 parts of thickening suspending agent; Wherein, the chromium zirconium corundum aggregate comprises the following components in parts by weight: 10 to 20 parts of a first granular material with a particle size of 4 mm ≤ ≤ 6 mm, 10 to 18 parts of a second granular material with a particle size of 2 mm ≤ < 4 mm, 10 to 18 parts of a third granular material with a particle size of 0.5 mm ≤ < 2 mm, and 20 to 28 parts of a fourth granular material with a particle size of < 0.5 mm; in parts by weight, the chemical composition of the first granular material, the second granular material, the third granular material and the fourth granular material comprises 15 to 60 parts of Cr2O3, 9 to 12 parts of ZrO2, 25 to 39 parts of Al2O3, 8 to 12 parts of SiO2 and 0.2 to 0.5 parts of Fe2O3; The mixed matrix powder comprises the following components in parts by weight: 22 to 28 parts of chromium powder with a particle size of ≤44 μm, 5 to 18 parts of Al2O3 powder with a particle size of ≤5 μm, 3 to 6 parts of zircon powder with a particle size of ≤2.5 μm, and 1 to 3 parts of kaolin.

2. The chromium-zirconium-corundum composite material according to claim 1, characterized in that: The preparation method of the chromium-zirconium corundum aggregate comprises the following steps: Prepare raw materials according to the chemical composition of the first pellet, the second pellet, the third pellet and the fourth pellet, The raw materials are wet ball-milled to prepare aggregate slurry; The aggregate slurry is subjected to filter pressing and vacuum slurry kneading, and then extruded into aggregate mud strips; The aggregate mud strips are dried and then calcined at a high temperature of 1560° C. to 1700° C., and then crushed to prepare the first granular material, the second granular material, the third granular material and the fourth granular material.

3. The chromium-zirconium-corundum composite material according to claim 1, characterized in that: The mixed matrix powder has one or more of the following characteristics: (1) The chemical composition of the chromium powder includes, by weight, 71 to 80 parts of Cr2O3, 5 to 10 parts of ZrO2, 2 to 8 parts of Al2O3, 2 to 10 parts of SiO2, and 0.2 to 0.5 parts of Fe2O3; (2) The chemical composition of the Al2O3-containing powder includes 96 to 99 parts of Al2O3 and 0 to 0.2 parts of Fe2O3 in parts by weight; (3) In parts by weight, the chemical composition of the zircon powder includes 62 to 65 parts of ZrO2, 32 to 35 parts of SiO2, 0.2 to 0.5 parts of Al2O3 and 0.05 to 0.3 parts of Fe2O3.

4. The chromium-zirconium-corundum composite material according to any one of claims 1 to 3, characterized in that: The dispersant is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate.

5. The chromium-zirconium-corundum composite material according to any one of claims 1 to 3, characterized in that: The thickening suspending agent is selected from one or more of sodium benzoate and attapulgite.

6. A method for preparing the chromium-zirconium-corundum composite material according to any one of claims 1 to 5, characterized in that: The following steps are involved: Take the raw materials according to weight proportions to prepare a mixed material; After dry mixing the mixed material, the dispersant, the thickening suspending agent and the solvent are added and mixed to prepare a wet material; The wet material is subjected to vacuum casting to prepare a molding blank; The chromium-zirconium-corundum composite material is prepared by drying and firing the molded blank.

7. The method for preparing the chromium-zirconium-corundum composite material according to claim 6, characterized in that: The process parameters of vacuum casting include: vacuum degree ≤-0.08MPa.

8. The method for preparing the chromium-zirconium-corundum composite material according to claim 6, characterized in that: The preparation method has one or more of the following characteristics: (1) The process parameters of the blank drying include: drying temperature of 40°C to 110°C, drying time ≥ 24h; (2) The firing process parameters include: heating the temperature to 1540°C to 1630°C at a heating rate of 5°C / h to 15°C / h, and keeping the temperature for 8h to 16h.

9. The method for preparing chromium-zirconium-corundum aggregate according to any one of claims 6 to 8, characterized in that: The following steps are involved: S1. Mix zircon sand, chromium oxide green and alumina powder according to weight proportions, add appropriate amount of water and mix and grind in a stirring ball mill for 3h to 5h to prepare aggregate slurry with a particle size of 2μm to 5μm, filter press, vacuum slurry, and extrusion into aggregate mud strips, air-dry and dry the aggregate mud strips, calcine at 1560℃ to 1700℃, and finally crush into first, second, third and fourth aggregates; S2. Select chromium powder with a particle size of ≤44μm, Al2O3 powder with a particle size of ≤5μm, zircon powder with a particle size of ≤2.5μm and kaolin to prepare a mixed matrix powder according to the weight ratio; S3. Select the first pellet, the second pellet, the third pellet and the fourth pellet in step S1 according to the weight ratio, and put the mixed matrix powder in step S2 into a medium-speed mixer and dry mix for 3min to 5min to prepare a mixed material; S4. Add dispersant and water to the mixed material in step S3, wet mix for 1min to 3min, then add thickening suspending agent, stir for 6min to 15min until the surface turns slurry, and prepare wet material; S5. The wet material of step S4 is injected into a vacuum mixer, evacuated for 5min to 15min until the vacuum degree is ≤-0.08MPa, and then injected into a plaster mold through a vacuum tube, and naturally dried for 24 to 48h, and then demolded and dried to prepare a molded blank; S6. Place the formed blank of step S5 in a drying kiln for drying at a temperature of 40 to 110°C for a drying time of ≥24 hours; fire the dried product, and during the firing process, heat it to 1540-1630°C at a heating rate of 5 to 15°C / h and keep it warm for 8 to 16 hours to prepare a chromium-zirconium-corundum composite material.

10. A corundum brick for glass kiln, characterized in that: The chromium-zirconium-corundum composite material comprises the chromium-zirconium-corundum composite material according to any one of claims 1 to 5.

Images