Zirconium silicate-containing composite material and application thereof in preparation of refractory material

Abstract

The invention belongs to the technical field of refractory materials, and particularly discloses a zirconium silicate-containing composite material and an application of the zirconium silicate-containing composite material in preparation of the refractory materials. Comprising the following components in parts by mass: 50-60 parts of zirconium silicate, 24-30 parts of modified zirconium silicate, 8-15 parts of pyrophyllite powder, 2-5 parts of a sintering aid, 0.5-2 parts of rare earth oxide and 0.5-2 parts of silicon dioxide aerogel. The zirconium silicate is used as a main body material, and under the combined action of the modified zirconium silicate, the pyrophyllite powder, the sintering aid, the rare earth oxide and the silicon dioxide aerogel, the composite material with excellent high temperature resistance, thermal shock resistance and erosion resistance is obtained.

Description

Technical Field

[0001] This invention relates to the field of refractory materials technology, specifically to a zirconium silicate-containing composite material and its application in the preparation of refractory materials. Background Technology

[0002] Refractory materials are indispensable key materials in high-temperature industries, widely used in high-temperature kilns, thermal equipment linings, and structural components in metallurgy, building materials, chemicals, and energy sectors. Their performance directly affects the operating efficiency, service life, and safe production of high-temperature equipment. As high-temperature industries develop towards higher efficiency, larger scale, and energy conservation, higher requirements are placed on the high-temperature resistance and thermal stability of refractory materials.

[0003] Zirconium silicate, as a high-quality refractory raw material, possesses characteristics such as high melting point, excellent chemical stability, resistance to high-temperature corrosion, and low thermal conductivity, and is widely used in the preparation of high-grade refractory materials. However, zirconium silicate alone has defects such as high brittleness, low flexural strength, and susceptibility to structural collapse at high temperatures, which limits its application in the high-end refractory field.

[0004] Therefore, this application is submitted. Summary of the Invention

[0005] This invention provides a zirconium silicate-containing composite material and its application in the preparation of refractory materials. The zirconium silicate-containing composite material of this invention has excellent high-temperature resistance, thermal shock resistance and corrosion resistance.

[0006] The present invention solves its technical problem by adopting the following technical solution: A zirconium silicate-containing composite material comprises the following components in parts by weight: 50-60 parts zirconium silicate, 24-30 parts modified zirconium silicate, 8-15 parts pyrophyllite powder, 2-5 parts sintering aid, 0.5-2 parts rare earth oxides, and 0.5-2 parts silica aerogel.

[0007] This application creatively combines the above-mentioned raw materials, with zirconium silicate as the main material. Under the combined action of modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides and silica aerogel, a composite material with excellent high temperature resistance, thermal shock resistance and corrosion resistance is obtained.

[0008] In a preferred embodiment of this application, the sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:(0.25~0.5).

[0009] This application uses cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:(0.25~0.5) as sintering aids, which can synergistically regulate the grain growth rate, avoid abnormal grain growth, and form a low-melting-point liquid phase that fills the pores and grain boundaries of the composite material. On the one hand, it promotes the wetting and fusion between particles and strengthens the grain boundary bonding strength. On the other hand, it can hinder the diffusion of oxygen at high temperatures and reduce the high-temperature oxidation loss of components such as zirconium silicate. This can promote the formation of a dense and uniform composite material and effectively improve the high-temperature resistance, thermal shock resistance and corrosion resistance of the composite material.

[0010] In a preferred embodiment of this application, the rare earth oxide is yttrium oxide.

[0011] As a preferred embodiment of this application, the method for preparing the modified zirconium silicate is as follows: (1) Add carbon nanotubes, graphite, and polyvinylpyrrolidone to N-methylpyrrolidone, stir evenly, then add phenolic resin, stir evenly at 65~80℃ to obtain modified liquid. (2) Add zirconium silicate, titanate coupling agent and oxalic acid to water and stir evenly to obtain a mixture; (3) Stir the modified liquid and the mixed liquid evenly, sonicate, centrifuge, filter, dry, and heat treat to obtain modified zirconium silicate.

[0012] This application uses carbon nanotubes, graphite, phenolic resin, and PVP as modifying agents. Zirconium silicate is treated with titanate coupling agent and oxalic acid, and then the modifying agent is used to coat and modify the zirconium silicate. After heat treatment, the phenolic resin forms a carbon coating layer, and the graphite and PVP generate graphene in situ. A carbon coating layer rich in graphene and carbon nanotubes is formed on the surface of zirconium silicate, which effectively inhibits grain boundary migration and abnormal grain growth, obtains a fine-grained structure, improves the interfacial interaction between modified zirconium silicate and zirconium silicate, and effectively improves the high temperature resistance, thermal shock resistance and corrosion resistance of the composite material.

[0013] As a preferred embodiment of this application, the mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin is 1:(0.2~0.5):(0.2~0.5):(5~10):(2~4).

[0014] As a preferred embodiment of this application, the mass ratio of zirconium silicate, titanate coupling agent, oxalic acid, and water is 1:(0.01~0.02):(0.02~0.04):(4~10).

[0015] As a preferred embodiment of this application, the titanate coupling agent is at least one of isopropyltristearate titanate, isopropyltriisostearate titanate, isopropyltrioleoyloxytitanate, and isopropyltris(dioctylpyrophosphate)titanate.

[0016] As a preferred embodiment of this application, the mass ratio of the modified liquid to the mixed liquid is 1:(4~10).

[0017] In a preferred embodiment of this application, the ultrasonic treatment power is 200~600W and the ultrasonic treatment time is 30~60min.

[0018] As a preferred embodiment of this application, the heat treatment temperature is 800~900℃ and the time is 1~4h.

[0019] This invention also provides a method for preparing a zirconium silicate-containing composite material, comprising the following steps: Zirconium silicate, modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides, and silica aerogel were ball-milled and mixed evenly, pressed into shape, and sintered to obtain a composite material containing zirconium silicate.

[0020] As a preferred embodiment of this application, the sintering temperature is 1580~1620℃ and the time is 2~6h.

[0021] The present invention also provides an application of a zirconium silicate-containing composite material in the preparation of refractory materials.

[0022] The beneficial effects of this invention: This application uses zirconium silicate as the main material, and with the combined action of modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides and silica aerogel, a composite material with excellent high temperature resistance, thermal shock resistance and corrosion resistance is obtained. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0025] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0026] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0027] Unless otherwise specified, all reagents or instruments used in this invention are commercially available conventional products. Unless otherwise specified, the raw materials used in each comparative example and the parallel experiments of each embodiment are the same commercially available products.

[0028] Example 1 A zirconium silicate-containing composite material comprises the following components in parts by weight: 53.3 parts zirconium silicate, 28 parts modified zirconium silicate, 12 parts pyrophyllite powder, 4 parts sintering aid, 1.5 parts yttrium oxide, and 1.2 parts silica aerogel.

[0029] The zirconium silicate has a particle size of 1250 mesh.

[0030] The pyrophyllite powder has a particle size of 300 mesh.

[0031] The average particle size of the yttrium oxide is 1 μm.

[0032] The silica aerogel is sourced from Jiayun New Materials, brand name SPS.

[0033] The sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:0.25.

[0034] The cryolite powder has a particle size of 200 mesh.

[0035] The method for preparing the modified zirconium silicate is as follows: (1) Carbon nanotubes, graphite, and polyvinylpyrrolidone were added to N-methylpyrrolidone and stirred at 200 rpm for 30 min. Then phenolic resin was added and stirred at 200 rpm for 30 min at 75°C to obtain a modified liquid. The mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin was 1:0.4:0.4:6:3.

[0036] (2) Add zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid to water and stir at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.02:0.02:6.

[0037] (3) The modified liquid and the mixture were stirred at 200 rpm for 30 min, treated with ultrasound at 400 W for 40 min, centrifuged at 3000 rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate. The mass ratio of the modified liquid to the mixture was 1:5.

[0038] The carbon nanotubes are sourced from Shanghai Xiangtian Nanotechnology, with the brand name XT-C1-02.

[0039] The graphite was sourced from Shanghai Xiangtian Nanomaterials, with the grade XT-C2-06.

[0040] The phenolic resin is sourced from Hebei Zetian Chemical Co., Ltd., and its brand name is 900A1.

[0041] The method for preparing the zirconium silicate-containing composite material includes the following steps: Zirconium silicate, modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides, and silica aerogel were ball-milled at 500 rpm for 1 hour, pressed into shape at 25 MPa, and sintered at 1600℃ for 4 hours to obtain a composite material containing zirconium silicate.

[0042] Example 2 A zirconium silicate-containing composite material comprises the following components in parts by weight: 54.5 parts zirconium silicate, 30 parts modified zirconium silicate, 8 parts pyrophyllite powder, 5 parts sintering aid, 0.5 parts yttrium oxide, and 2 parts silica aerogel.

[0043] The zirconium silicate has a particle size of 1250 mesh.

[0044] The pyrophyllite powder has a particle size of 300 mesh.

[0045] The average particle size of the yttrium oxide is 1 μm.

[0046] The silica aerogel is sourced from Jiayun New Materials, brand name SPS.

[0047] The sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:0.25.

[0048] The cryolite powder has a particle size of 200 mesh.

[0049] The method for preparing the modified zirconium silicate is as follows: (1) Carbon nanotubes, graphite, and polyvinylpyrrolidone were added to N-methylpyrrolidone and stirred at 200 rpm for 30 min. Then phenolic resin was added and stirred at 200 rpm for 30 min at 75°C to obtain a modified liquid. The mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin was 1:0.4:0.4:6:3.

[0050] (2) Add zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid to water and stir at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.02:0.02:6.

[0051] (3) The modified liquid and the mixture were stirred at 200 rpm for 30 min, treated with ultrasound at 400 W for 40 min, centrifuged at 3000 rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate. The mass ratio of the modified liquid to the mixture was 1:5.

[0052] The carbon nanotubes are sourced from Shanghai Xiangtian Nanotechnology, with the brand name XT-C1-02.

[0053] The graphite was sourced from Shanghai Xiangtian Nanomaterials, with the grade XT-C2-06.

[0054] The phenolic resin is sourced from Hebei Zetian Chemical Co., Ltd., and its brand name is 900A1.

[0055] The method for preparing the zirconium silicate-containing composite material includes the following steps: Zirconium silicate, modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides, and silica aerogel were ball-milled at 500 rpm for 1 hour, pressed into shape at 25 MPa, and sintered at 1600℃ for 4 hours to obtain a composite material containing zirconium silicate.

[0056] Example 3 A zirconium silicate-containing composite material comprises the following components in parts by weight: 56.5 parts zirconium silicate, 24 parts modified zirconium silicate, 15 parts pyrophyllite powder, 2 parts sintering aid, 2 parts yttrium oxide, and 0.5 parts silica aerogel.

[0057] The zirconium silicate has a particle size of 1250 mesh.

[0058] The pyrophyllite powder has a particle size of 300 mesh.

[0059] The average particle size of the yttrium oxide is 1 μm.

[0060] The silica aerogel is sourced from Jiayun New Materials, brand name SPS.

[0061] The sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:0.25.

[0062] The cryolite powder has a particle size of 200 mesh.

[0063] The method for preparing the modified zirconium silicate is as follows: (1) Carbon nanotubes, graphite, and polyvinylpyrrolidone were added to N-methylpyrrolidone and stirred at 200 rpm for 30 min. Then phenolic resin was added and stirred at 200 rpm for 30 min at 75°C to obtain a modified liquid. The mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin was 1:0.4:0.4:6:3.

[0064] (2) Add zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid to water and stir at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.02:0.02:6.

[0065] (3) The modified liquid and the mixture were stirred at 200 rpm for 30 min, treated with ultrasound at 400 W for 40 min, centrifuged at 3000 rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate. The mass ratio of the modified liquid to the mixture was 1:5.

[0066] The carbon nanotubes are sourced from Shanghai Xiangtian Nanotechnology, with the brand name XT-C1-02.

[0067] The graphite was sourced from Shanghai Xiangtian Nanomaterials, with the grade XT-C2-06.

[0068] The phenolic resin is sourced from Hebei Zetian Chemical Co., Ltd., and its brand name is 900A1.

[0069] The method for preparing the zirconium silicate-containing composite material includes the following steps: Zirconium silicate, modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides, and silica aerogel were ball-milled at 500 rpm for 1 hour, pressed into shape at 25 MPa, and sintered at 1600℃ for 4 hours to obtain a composite material containing zirconium silicate.

[0070] Example 4 A zirconium silicate-containing composite material comprises the following components in parts by weight: 53.3 parts zirconium silicate, 28 parts modified zirconium silicate, 12 parts pyrophyllite powder, 4 parts sintering aid, 1.5 parts yttrium oxide, and 1.2 parts silica aerogel.

[0071] The zirconium silicate has a particle size of 1250 mesh.

[0072] The pyrophyllite powder has a particle size of 300 mesh.

[0073] The average particle size of the yttrium oxide is 1 μm.

[0074] The silica aerogel is sourced from Jiayun New Materials, brand name SPS.

[0075] The sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:0.5.

[0076] The cryolite powder has a particle size of 200 mesh.

[0077] The method for preparing the modified zirconium silicate is as follows: (1) Carbon nanotubes, graphite, and polyvinylpyrrolidone were added to N-methylpyrrolidone and stirred at 200 rpm for 30 min. Then phenolic resin was added and stirred at 200 rpm for 30 min at 75°C to obtain a modified liquid. The mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin was 1:0.4:0.4:6:3.

[0078] (2) Add zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid to water and stir at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.01:0.04:6.

[0079] (3) The modified liquid and the mixture were stirred at 200 rpm for 30 min, treated with ultrasound at 400 W for 40 min, centrifuged at 3000 rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate. The mass ratio of the modified liquid to the mixture was 1:5.

[0080] The carbon nanotubes are sourced from Shanghai Xiangtian Nanotechnology, with the brand name XT-C1-02.

[0081] The graphite was sourced from Shanghai Xiangtian Nanomaterials, with the grade XT-C2-06.

[0082] The phenolic resin is sourced from Hebei Zetian Chemical Co., Ltd., and its brand name is 900A1.

[0083] The method for preparing the zirconium silicate-containing composite material includes the following steps: Zirconium silicate, modified zirconium silicate, pyrophyllite powder, sintering aid, rare earth oxides, and silica aerogel were ball-milled at 500 rpm for 1 hour, pressed into shape at 25 MPa, and sintered at 1600℃ for 4 hours to obtain a composite material containing zirconium silicate.

[0084] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses an equal amount of zirconium silicate to replace the modified zirconium silicate, while everything else is the same.

[0085] A zirconium silicate-containing composite material comprises the following components in parts by weight: 81.3 parts zirconium silicate, 12 parts pyrophyllite powder, 4 parts sintering aid, 1.5 parts yttrium oxide, and 1.2 parts silica aerogel.

[0086] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the preparation method of the modified zirconium silicate is different, but everything else is the same.

[0087] The method for preparing the modified zirconium silicate is as follows: (1) Zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid are added to water and stirred at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.02:0.02:6.

[0088] (2) The mixture was treated with ultrasound at 400W for 40 min, centrifuged at 3000rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate.

[0089] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the preparation method of the modified zirconium silicate is different, but everything else is the same.

[0090] The method for preparing the modified zirconium silicate is as follows: (1) Carbon nanotubes were added to N-methylpyrrolidone and stirred at 200 rpm for 30 min to obtain a modified solution; the mass ratio of carbon nanotubes to N-methylpyrrolidone was 1:6.

[0091] (2) Add zirconium silicate with a particle size of 1250 mesh, isopropyltrioleoyl oxytitanate, and oxalic acid to water and stir at 200 rpm for 30 min to obtain a mixture; the mass ratio of zirconium silicate, isopropyltrioleoyl oxytitanate, oxalic acid, and water is 1:0.02:0.02:6.

[0092] (3) The modified liquid and the mixture were stirred at 200 rpm for 30 min, treated with ultrasound at 400 W for 40 min, centrifuged at 3000 rpm for 10 min, filtered, dried, and heat-treated at 850℃ for 2 h to obtain modified zirconium silicate. The mass ratio of the modified liquid to the mixture was 1:5.

[0093] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the sintering aids are different.

[0094] A zirconium silicate-containing composite material comprises the following components in parts by weight: 53.3 parts zirconium silicate, 28 parts modified zirconium silicate, 12 parts pyrophyllite powder, 4 parts sintering aid, 1.5 parts yttrium oxide, and 1.2 parts silica aerogel.

[0095] The sintering aid is 200-mesh cryolite powder.

[0096] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the sintering aids are different.

[0097] A zirconium silicate-containing composite material comprises the following components in parts by weight: 53.3 parts zirconium silicate, 28 parts modified zirconium silicate, 12 parts pyrophyllite powder, 4 parts sintering aid, 1.5 parts yttrium oxide, and 1.2 parts silica aerogel.

[0098] The sintering aid is ethylenediaminetetraacetic acid.

[0099] Test case 1. Thermal shock resistance test (residual strength retention rate): The test shall be conducted in accordance with the standard GB / T30873-2014.

[0100] 2. Corrosion resistance test (corrosion rate): The test shall be conducted in accordance with the GB / T8931-2007 standard.

[0101] 3. High temperature resistance test (permanent linear change after heating at 1200℃ for 8h): Refer to GB / T 17911-2018.

[0102] Table 1

[0103] As can be seen from Table 1, the zirconium silicate composite material described in this invention has excellent high temperature resistance, thermal shock resistance and corrosion resistance, and has broad application prospects.

[0104] Comparing Example 1 with Comparative Examples 1-3, it can be seen that the modified zirconium silicate described in this application can significantly improve the high temperature resistance, thermal shock resistance, and corrosion resistance of the composite material. Moreover, the modified zirconium silicate prepared by different methods has different effects on the improvement of high temperature resistance, thermal shock resistance, and corrosion resistance. The modified zirconium silicate prepared by the modification method described in this application can significantly improve the high temperature resistance, thermal shock resistance, and corrosion resistance.

[0105] Comparing Example 1 with Comparative Examples 4-5, it can be seen that the sintering aid of cryolite powder and ethylenediaminetetraacetic acid in the present application at a mass ratio of 1:(0.25-0.5) significantly improves the high temperature resistance, thermal shock resistance and corrosion resistance.

[0106] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A zirconium silicate-containing composite material, characterized in that, The components include the following parts by weight: 50-60 parts zirconium silicate, 24-30 parts modified zirconium silicate, 8-15 parts pyrophyllite powder, 2-5 parts sintering aid, 0.5-2 parts rare earth oxides, and 0.5-2 parts silica aerogel.

2. The zirconium silicate-containing composite material according to claim 1, characterized in that, The sintering aid comprises cryolite powder and ethylenediaminetetraacetic acid in a mass ratio of 1:(0.25~0.5).

3. The zirconium silicate-containing composite material according to claim 1, characterized in that, The rare earth oxide is yttrium oxide.

4. The zirconium silicate-containing composite material according to claim 1, characterized in that, The method for preparing the modified zirconium silicate is as follows: (1) Add carbon nanotubes, graphite, and polyvinylpyrrolidone to N-methylpyrrolidone, stir evenly, then add phenolic resin, stir evenly at 65~80℃ to obtain modified liquid. (2) Add zirconium silicate, titanate coupling agent and oxalic acid to water and stir evenly to obtain a mixture; (3) Stir the modified liquid and the mixed liquid evenly, sonicate, centrifuge, filter, dry, and heat treat to obtain modified zirconium silicate.

5. The zirconium silicate-containing composite material according to claim 4, characterized in that, The mass ratio of carbon nanotubes, graphite, polyvinylpyrrolidone, N-methylpyrrolidone, and phenolic resin is 1:(0.2~0.5):(0.2~0.5):(5~10):(2~4).

6. The zirconium silicate-containing composite material according to claim 4, characterized in that, The mass ratio of zirconium silicate, titanate coupling agent, oxalic acid, and water is 1:(0.01~0.02):(0.02~0.04):(4~10).

7. The zirconium silicate-containing composite material according to claim 4, characterized in that, The titanate coupling agent is at least one of isopropyltristearate titanate, isopropyltriisostearate titanate, isopropyltrioleoyloxytitanate, and isopropyltris(dioctylpyrophosphate)titanate.

8. The zirconium silicate-containing composite material according to claim 4, characterized in that, The mass ratio of the modified liquid to the mixed liquid is 1:(4~10).

9. The zirconium silicate-containing composite material according to claim 4, characterized in that, The ultrasonic treatment power is 200~600W, and the ultrasonic treatment time is 30~60min.

10. The application of the zirconium silicate composite material according to any one of claims 1 to 9 in the preparation of refractory materials.

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