CN112811920A - Ultrahigh-temperature refractory composite material and preparation method thereof - Google Patents
Ultrahigh-temperature refractory composite material and preparation method thereof Download PDFInfo
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Abstract
The ultra-high temperature refractory composite material mainly comprises the following components in parts by mass: 40-50 parts of mullite microspheres, 10-15 parts of bauxite chamotte, 10-15 parts of calcium titanium aluminate, 5-10 parts of Guangxi white mud, 5-10 parts of silica sol, 2-5 parts of active alpha-Al 2O3 micro powder, 2-5 parts of a bonding agent and 2-5 parts of an additive; the bonding agent is aluminum dihydrogen phosphate solution, and the additive is AlF3·3H2O and V2O5. The ultrahigh-temperature refractory composite material and the preparation method thereof have the advantages of reasonable formula setting, excellent fire resistance, low heat conductivity coefficient, good thermal shock resistance, improvement of alkali gas phase erosion resistance and strength of the refractory composite material, simple preparation process, easy large-scale production, good economic benefit and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of refractory composite materials, and particularly relates to an ultrahigh-temperature refractory composite material and a preparation method thereof.
Background
At present, energy sources are increasingly tense and the environment is increasingly worsened, and energy conservation and emission reduction are key technologies for national economy and social sustainable development. Among them, the research on the refractory materials for heat insulation and heat preservation is one of the key problems in the development of energy-saving technology, and the research on the aspects of new material systems, new preparation technology, improvement of service performance and the like becomes a research hotspot and leading-edge subject in the field of energy saving and environmental protection.
The refractory material is generally applied to the heat-insulating layer of the heat-insulating kiln furnace in ferrous metallurgy and the like, and has the characteristics of low heat conductivity, high apparent porosity, low volume density and the like. The heat-insulating layer made of the refractory material and arranged on the outer side of the working lining can effectively reduce the heat loss of the thermal kiln, and makes an important contribution to the industrial production for achieving the purposes of energy conservation and emission reduction. There are various types of refractory materials, wherein the heat-insulating refractory materials can be classified into three types according to the use temperature: (1) low-temperature refractory material, the use temperature is less than 600 ℃; (2) the medium-temperature refractory material is used at the temperature of 600-1200 ℃; (3) the high-temperature refractory material has the use temperature of 1200 ℃.
At present, the refractory material in the prior art is often built into a permanent layer with a certain thickness when in use due to poor mechanical property and low working temperature. In order to further improve the mechanical property and the service performance of the refractory material, the thickness of a permanent layer and a heat insulation layer can be reduced, the weight of a furnace body is reduced, and the method has important significance for effectively utilizing the existing resources. Therefore, it is necessary to develop an ultra-high temperature refractory composite material and a preparation process thereof to solve the above technical problems.
Chinese patent application No. CN201910704295.3 discloses a fire-resistant composite material and a preparation method thereof, wherein 4-8 parts of perfluoroalkyl triazine rubber emulsion, 9-15 parts of calcium carbonate, 7-15 parts of glass fiber, 5-8 parts of chloroprene rubber emulsion, 14-18 parts of titanium nitride, 8-12 parts of carbon fiber and 35-45 parts of liquid phenolic resin raw materials are weighed according to parts by weight, so as to prepare the fire-resistant composite material with low density, high specific strength and wear resistance, and the fire resistance and the like of the fire-resistant composite material are required to be further improved.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide the ultrahigh-temperature refractory composite material and the preparation method thereof, the formula is reasonable in arrangement, the ultrahigh-temperature refractory composite material has excellent fire resistance, low thermal conductivity and good thermal shock resistance, the alkali gas phase erosion resistance and strength of the refractory composite material are improved, the preparation process is simple, the large-scale production is easy, the economic benefit is good, and the application prospect is wide.
The purpose of the invention is realized by the following technical scheme:
an ultrahigh-temperature refractory composite material mainly comprises the following components in parts by weight: 40-50 parts of mullite microspheres, 10-15 parts of bauxite chamotte, 10-15 parts of calcium titanium aluminate, 5-10 parts of Guangxi white mud, 5-10 parts of silica sol and active alpha-Al2O32-5 parts of micro powder, 2-5 parts of a binding agent and 2-5 parts of an additive; the binding agent isAluminum dihydrogen phosphate solution, wherein the additive is AlF3·3H2O and V2O5。
The ultrahigh-temperature refractory composite material is reasonable in formula arrangement, takes mullite microspheres, high-alumina bauxite clinker, calcium titanium aluminate and Guangxi white mud as aggregates, and takes silica sol and active alpha-Al2O3The micro powder is fine powder, the aluminum dihydrogen phosphate solution is a bonding agent, and AlF3·3H2O and V2O5The additive is good in synergistic effect, excellent in fire resistance, low in heat conductivity coefficient and good in thermal shock resistance, and the alkali gas phase corrosion resistance and strength of the refractory composite material are improved.
Firstly, mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud are used as aggregates, the compounding effect is good, and the refractory composite material has excellent volume stability and sintering performance and high refractoriness. The surface of the mullite microsphere presents a mullite columnar interweaving structure, crystals are uniformly distributed and tightly connected, the interweaving structure forms a three-dimensional framework structure, so that the amount of pores among the crystals can be increased, the sizes of pores are small, the pores are the same and are uniformly distributed, the thermal conductivity is lower, the strength of the fireproof composite material can be improved, and the mullite microsphere is suitable for serving as porous aggregate; the special-grade high-alumina bauxite clinker is composed of corundum, mullite and a small amount of glass phase, has better sintering compatibility with titanium calcium aluminate, and can improve the mechanical strength, the thermal shock resistance and the alkaline gas corrosion resistance by compounding the corundum and the mullite. Wherein the calcium titanium aluminate is CA obtained by treating waste residues generated by smelting ferrotitanium through the processes of iron removal, silicon reduction, homogenization, melting and the like6And Ca ((Al)0.84Ti0.16)2)6O19As a main crystal phase, with CA2、CaTiO3Corundum and Rutile are complex phase refractory raw materials of a secondary crystal phase, are low in cost, and have high strength, high melting point, high refractoriness, low thermal conductivity and low thermal expansion coefficient. When potassium gas reacts with anorthite in calcium titanium aluminate to generate a liquid phase of a calcium-silicon-potassium system, the liquid phase can further hinder the gas from entering; potassium gas can be deposited in pores inside the calcium titanium aluminate particles, thereby playing a good roleResisting the corrosion of alkaline gas. The titanium calcium aluminate is adopted, which plays a positive role in recycling the solid wastes in the alloy smelting.
By sol, active alpha-Al2O3The micro powder is taken as fine powder, is gathered in pores between aggregates and is matched with a bonding agent aluminum dihydrogen phosphate solution, so that the bonding force between the aggregates is favorably improved, the gas phase substance is effectively weakened to permeate into the refractory composite material, and the alkali gas phase erosion resistance and the integral strength of the refractory composite material are improved. By AlF3·3H2O and V2O5The addition of the mullite whisker can lead the refractory composite material to generate the mullite whisker in situ at 1200 ℃, and can effectively improve the compactness, the normal temperature strength and the high temperature strength of the sample.
Further, the mullite microspheres mainly comprise the following chemical components in percentage by mass: al (Al)2O362.35％，SiO231.85％，TiO22.82％，Fe2O31.5％，CaO0.15％，MgO0.12％，K2O0.19％，Na20.05 percent of O; the glass phase content of the mullite microspheres is 15.12%.
The mullite crystals are well developed, the mullite crystals are filled with the increased content of the internal glass phase, the glass phase has a sealing effect, the connection between internal pores and the outside is reduced, the number of open pores is reduced, the number of closed pores is increased, the open pores are mainly used for convection heat transfer, the closed pores are mainly used for heat conduction, the heat transfer capacity of the convection heat transfer is stronger, and therefore the increase of the closed pores is beneficial to reducing the heat conductivity coefficient of a sample and increasing the heat insulation effect of the sample. The mullite crystal has a refractoriness of more than 1790 ℃ and a thermal conductivity coefficient of 0.245W/(m.k) at 800 ℃.
Further, the above ultra-high temperature refractory composite material, the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 4-5: 1-2.
Furthermore, in the ultrahigh-temperature refractory composite material, the average grain diameter of the mullite microspheres is 0.1-0.2mm, and the bauxite is calcinedThe average grain diameter of the material is 25-50 μm, and the average grain diameter of the calcium titanium aluminate is 0.5-2 mm; the average grain diameter of the Guangxi white mud is 30-60 mu m, the average grain diameter of the silica sol is 10-30 mu m, and the active alpha-Al2O3The average particle size of the micro powder is 1-3 μm; the average particle size of the additive is 40-50 μm.
Furthermore, the ultrahigh-temperature refractory composite material and the refractory composite material mainly comprise the following components in parts by mass: 42 parts of mullite microspheres, 14 parts of bauxite chamotte, 12 parts of calcium titanium aluminate, 6 parts of Guangxi white mud, 7 parts of silica sol and active alpha-Al2O35 parts of micro powder, 3 parts of a bonding agent and 4 parts of an additive.
The invention also relates to the ultrahigh-temperature refractory composite material and a preparation method thereof, and the preparation method comprises the following steps:
(1) mixing materials: preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.5-1h, and then adding silica sol and active alpha-Al2O3Carrying out dry mixing on the micro powder and the bonding agent in a mixing barrel for 0.1-0.2h, finally adding the additive, and mixing for 3-5min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 100 ℃ and 110 ℃ for 20-28 h;
(4) roasting: and (4) placing the dried blank into a resistance furnace for roasting to obtain the refractory composite material.
Further, in the ultra-high temperature refractory composite material and the preparation method thereof, after the blank material is roasted and dried in the step (4) is placed into the resistance furnace, the temperature of the resistance furnace is firstly increased to 550-600 ℃ at a rate of 3-5 ℃/min, the temperature is kept at 550-600 ℃ for 1-1.5 h, then increased to 1150-1300 ℃ at a rate of 5-7 ℃/min, the temperature is kept at 0.2-0.5 h, the temperature is increased to 1400-1500 ℃ at a rate of 3-5 ℃/min, and the temperature is kept at 2.5-3.0 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ultrahigh-temperature refractory composite material disclosed by the invention is reasonable in formula arrangement, takes mullite microspheres, high-alumina bauxite clinker, calcium titanium aluminate and Guangxi white mud as aggregates, silica sol and active alpha-Al2O3The micro powder is fine powder, the aluminum dihydrogen phosphate solution is a bonding agent, and AlF3·3H20 and V2O5The additive is good in synergistic effect, has excellent fire resistance, low heat conductivity coefficient and good thermal shock resistance, and improves the alkali gas phase erosion resistance and strength of the refractory composite material;
(2) according to the ultrahigh-temperature refractory composite material disclosed by the invention, the bauxite chamotte and the titanium calcium aluminate have better sintering compatibility, the mechanical strength, the thermal shock resistance and the alkaline gas corrosion resistance can be improved by compounding the bauxite chamotte and the titanium calcium aluminate, the titanium calcium aluminate is low in cost, and the titanium calcium aluminate plays a positive role in recycling the solid wastes generated in the alloy smelting;
(3) the ultrahigh-temperature refractory composite material and the preparation method thereof provided by the invention have the advantages of simple preparation method, high flexibility, capability of being used for large-scale production and better economy.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention are clearly and completely described in the embodiments with reference to specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following embodiment provides an ultrahigh-temperature refractory composite material and a preparation method thereof, wherein the refractory composite material mainly comprises the following components in parts by weight: 40-50 parts of mullite microspheres, 10-15 parts of bauxite chamotte, 10-15 parts of calcium titanium aluminate, 5-10 parts of Guangxi white mud, 5-10 parts of silica sol and active alpha-Al2O32-5 parts of micro powder, 2-5 parts of a binding agent and 2-5 parts of an additive; the bonding agent is aluminum dihydrogen phosphate solution, and the additive is AlF3·3H20 and V2O5。
Further, the mullite microspheres mainly comprise the following chemical components in percentage by mass: al (Al)2O362.35％，SiO231.85％，TiO22.82％，Fe2O31.5％，CaO0.15％，MgO0.12％，K2O0.19％，Na20.05 percent of O; the glass phase content of the mullite microspheres is 15.12%.
Further, the average grain size of the mullite microspheres is 0.1-0.2mm, the average grain size of the bauxite chamotte is 25-50 mu m, and the average grain size of the calcium titanium aluminate is 0.5-2 mm; the average grain diameter of the Guangxi white mud is 30-60 mu m, the average grain diameter of the silica sol is 10-30 mu m, and the active alpha-Al2O3The average particle size of the micro powder is 1-3 μm; the average particle size of the additive is 40-50 μm.
Example 1
(1) Mixing materials: the fireproof composite material mainly comprises the following components in parts by weight: 50 parts of mullite microspheres, 10 parts of bauxite chamotte, 12 parts of calcium titanium aluminate, 8 parts of Guangxi white mud, 5 parts of silica sol and active alpha-Al2O35 parts of micro powder, 3 parts of a binding agent and 2 parts of an additive; the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 4: 1; preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.5h, and then adding silica sol and active alpha-Al2O3Carrying out dry mixing on the micro powder and the bonding agent in a mixing barrel for 0.2h, and finally adding the additive to mix for 3min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 110 ℃ for 24 h;
(4) roasting: and (3) after the dried blank is placed into a resistance furnace, heating the resistance furnace to 600 ℃ at a speed of 3 ℃/min, keeping the temperature of 600 ℃ for 1.0h, heating to 1300 ℃ at a speed of 7 ℃/min, keeping the temperature for 0.3h, heating to 1450 ℃ at a speed of 5 ℃/min, and keeping the temperature for 2.5h to obtain the refractory composite material.
Example 2
(2) Mixing materials: the fireproof composite material mainly comprises the following components in parts by weight: 42 parts of mullite microspheres, 12 parts of bauxite chamotte, 11 parts of calcium titanium aluminate, 6 parts of Guangxi white mud, 6 parts of silica sol and active alpha-Al2O35 parts of micro powder, 4 parts of binding agent and 4 parts of additive; the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 5: 1.5; preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.5h, and then adding silica sol and active alpha-Al2O3Carrying out dry mixing on the micro powder and the bonding agent in a mixing barrel for 0.1h, and finally adding the additive to mix for 3min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 110 ℃ for 24 h;
(4) roasting: and (3) after the dried blank is placed into a resistance furnace, heating the resistance furnace to 600 ℃ at a speed of 3 ℃/min, keeping the temperature of 600 ℃ for 1.0h, heating to 1300 ℃ at a speed of 5 ℃/min, keeping the temperature for 0.3h, heating to 1450 ℃ at a speed of 3 ℃/min, and keeping the temperature for 2.5h to obtain the refractory composite material.
Example 3
(3) Mixing materials: the fireproof composite material mainly comprises the following components in parts by weight: 40 parts of mullite microspheres, 15 parts of bauxite chamotte, 15 parts of titanium calcium aluminate, 5 parts of Guangxi white mud, 10 parts of silica sol and active alpha-Al2O35 parts of micro powder, 5 parts of a binding agent and 4 parts of an additive; the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 5: 1.8; preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.6h, and then adding silica sol and active alpha-Al2O3Continuously dry-mixing the micropowder and the binder in a mixing barrel for 0.1h, finally adding the additive, and mixing for 5min to obtain a mixture；
(2) Pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 110 ℃ for 24 h;
(4) roasting: and (3) after the dried blank is placed into a resistance furnace, the resistance furnace is heated to 600 ℃ at a speed of 4 ℃/min, the temperature is kept constant for 1.0h at 600 ℃, then is heated to 1300 ℃ at a speed of 6 ℃/min, the temperature is kept constant for 0.3h, is heated to 1450 ℃ at a speed of 3 ℃/min, and the temperature is kept constant for 2.5h, so that the refractory composite material is obtained.
Example 4
(4) Mixing materials: the fireproof composite material mainly comprises the following components in parts by weight: 48 parts of mullite microspheres, 12 parts of bauxite chamotte, 12 parts of calcium titanium aluminate, 8 parts of Guangxi white mud, 6 parts of silica sol and active alpha-Al2O34 parts of micro powder, 4 parts of binding agent and 3 parts of additive; the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 4: 1.5; preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.6h, and then adding silica sol and active alpha-Al2O3Carrying out dry mixing on the micro powder and the bonding agent in a mixing barrel for 0.1h, finally adding the additive, and mixing for 5min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 110 ℃ for 24 h;
(4) roasting: and (3) after the dried blank is placed into a resistance furnace, the resistance furnace is heated to 600 ℃ at a speed of 5 ℃/min, the temperature is kept constant for 1.0h at 600 ℃, then is heated to 1300 ℃ at a speed of 7 ℃/min, the temperature is kept constant for 0.3h, is heated to 1450 ℃ at a speed of 3 ℃/min, and the temperature is kept constant for 2.5h, so that the refractory composite material is obtained.
Example 5
(5) Mixing materials: 42 parts of mullite microspheres, 14 parts of bauxite chamotte, 12 parts of calcium titanium aluminate, 6 parts of Guangxi white mud, 7 parts of silica sol and active alpha-Al2O35 parts of micro powder, 3 parts of a binding agent and 4 parts of an additive; the AlF3·3H2O and V2O5The mass ratio of (A) to (B) is 4: 1; preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.5h, and then adding silica sol and active alpha-Al2O3Carrying out dry mixing on the micro powder and the bonding agent in a mixing barrel for 0.1h, finally adding the additive, and mixing for 5min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 110 ℃ for 24 h;
(4) roasting: and (3) after the dried blank is placed into a resistance furnace, the resistance furnace is heated to 600 ℃ at a speed of 5 ℃/min, the temperature is kept constant for 1.0h at 600 ℃, then is heated to 1300 ℃ at a speed of 7 ℃/min, the temperature is kept constant for 0.3h, is heated to 1450 ℃ at a speed of 3 ℃/min, and the temperature is kept constant for 2.5h, so that the refractory composite material is obtained.
Effect verification:
the performance test was carried out on the ultra high temperature refractory composite materials obtained in the above examples 1, 2, 3, 4 and 5 according to the following criteria, and the test results are shown in tables 1 and 2.
(1) The apparent porosity and the bulk density of the ultra-high temperature refractory composite samples obtained in the above examples 1, 2, 3, 4 and 5 were measured by the archimedes principle;
(2) the compression strength of the ultra-high temperature refractory composite samples obtained in the above examples 1, 2, 3, 4 and 5 was tested according to GB/T5072.2.2004 NIJ;
(3) recording the pre-firing mass and the post-firing mass of the ultra-high temperature refractory composite samples obtained in the above examples 1, 2, 3, 4 and 5, and calculating the mass change rate after heat treatment according to the formula;
(4) the pre-firing diameter and the post-firing diameter of the ultra-high temperature refractory composite samples obtained in example 1, example 2, example 3, example 4 and example 5 were recorded, and the linear change rate after the heat treatment was calculated from the formula.
(5) The thermal conductivity of the ultra-high temperature refractory composite samples obtained in examples 1, 2, 3, 4 and 5 was measured at 300 ℃, 500 ℃, 800 ℃ and 1000 ℃ according to YB/T4130.2005.
TABLE 1 sample Performance test results
TABLE 2 sample thermal conductivity Performance test results
In addition, the alkali gas resistance test was performed on the ultra-high temperature refractory composite materials obtained in the above examples 1, 2, 3, 4 and 5, and the test procedure was as follows: (1) mixing potassium carbonate powder and charcoal powder in a ratio of 1: 1 mass percent premixing;
(2) placing the samples of the ultra-high temperature refractory composite materials obtained in the above examples 1, 2, 3, 4 and 5 in a graphite crucible filled with a mixture of potassium carbonate powder and charcoal powder; (3) after the graphite crucible is placed into an alumina sagger with coke fully spread at the bottom, the graphite crucible is buried by the coke, and alumina micro powder is spread on the upper layer of the coke; (4) the alumina sagger was put into a high temperature furnace, and the furnace was cooled after the heat preservation at 1000 ℃ for 10 hours, and the eroded samples of the ultra-high temperature refractory composite material obtained in examples 1, 2, 3, 4 and 5 were tested for compressive strength, mass change rate and linear change rate.
The test results are shown in tables 3 and 4
TABLE 3 sample Performance test results after alkaline gas resistance test
TABLE 4 sample thermal conductivity coefficient Performance test results after alkaline gas resistance experiment
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (7)
1. The ultrahigh-temperature refractory composite material is characterized by mainly comprising the following components in parts by mass: 40-50 parts of mullite microspheres, 10-15 parts of bauxite chamotte, 10-15 parts of calcium titanium aluminate, 5-10 parts of Guangxi white mud, 5-10 parts of silica sol and active alpha-Al2O32-5 parts of micro powder, 2-5 parts of a binding agent and 2-5 parts of an additive; the bonding agent is aluminum dihydrogen phosphate solution, and the additive is AlF3·3H2O and V2O5。
2. The ultrahigh-temperature refractory composite material according to claim 1, wherein the mullite microspheres are mainly composed of the following chemical components in percentage by mass: al (Al)2O3，62.35%，SiO231.85%，TiO22.82%， Fe2O31.5%，CaO0.15%，MgO0.12%，K2O0.19%，Na20.05 percent of O; the glass phase content of the mullite microspheres is 15.12%.
3. The ultra high temperature refractory composite of claim 1, wherein the AlF is3·3H20 and V2O5The mass ratio of (A) to (B) is 4-5: 1-2.
4. The ultra-high temperature refractory composite material according to claim 1, wherein the mullite microspheres have an average particle size of 0.1-0.2mm, the bauxite clinker has an average particle size of 25-50 μm, and the calcium titanoaluminate has an average particle size of 0.5-2 mm; the average particle size of the Guangxi white mud is 30-60 mu m, the average particle size of the silica sol is 10-30 mu m, and the average particle size of the active alpha-Al 2O3 micro powder is 1-3 mu m; the average particle size of the additive is 40-50 μm.
5. The ultrahigh-temperature refractory composite material according to claim 1, consisting essentially of, in parts by mass: 42 parts of mullite microspheres, 14 parts of bauxite chamotte, 12 parts of calcium titanium aluminate, 6 parts of Guangxi white mud, 7 parts of silica sol and active alpha-Al2O35 parts of micro powder, 3 parts of a bonding agent and 4 parts of an additive.
6. The method for preparing the ultra-high temperature refractory composite according to any one of claims 1 to 5, comprising the steps of:
(1) mixing materials: preparing materials according to the formula; dry-mixing mullite microspheres, bauxite chamotte, calcium titanium aluminate and Guangxi white mud in a mixing barrel for 0.5-1h, adding silica sol, active alpha-Al 2O3 micro powder and a bonding agent, continuously dry-mixing in the mixing barrel for 0.1-0.2h, finally adding an additive, and mixing for 3-5min to obtain a mixture;
(2) pressing the material into a mold: loading the mixture into a die, and performing mechanical pressing forming on the mixture on a hydraulic testing machine under the condition of 170MPa to obtain a blank;
(3) drying: drying the blank in an oven at the drying temperature of 100 ℃ and 110 ℃ for 20-28 h;
(4) roasting: and (4) placing the dried blank into a resistance furnace for roasting to obtain the refractory composite material.
7. The preparation method of the ultrahigh-temperature refractory composite material as claimed in claim 6, wherein after the blank obtained by roasting and drying in the step (4) is placed in a resistance furnace, the temperature of the resistance furnace is raised to 550-600 ℃ at 3-5 ℃/min, the temperature is kept constant at 550-600 ℃ for 1-1.5 h, then raised to 1150-1300 ℃ at 5-7 ℃/min, the temperature is kept constant for 0.2-0.5 h, raised to 1400-1500 ℃ at 3-5 ℃/min, and the temperature is kept constant for 2.5-3.0 h.
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