CN111662090A - Magnesium aluminate spinel-silicon carbide-aluminum composite refractory material - Google Patents

Magnesium aluminate spinel-silicon carbide-aluminum composite refractory material Download PDF

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CN111662090A
CN111662090A CN202010645685.0A CN202010645685A CN111662090A CN 111662090 A CN111662090 A CN 111662090A CN 202010645685 A CN202010645685 A CN 202010645685A CN 111662090 A CN111662090 A CN 111662090A
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silicon carbide
magnesia
alumina
spinel
alumina spinel
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CN111662090B (en
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李红霞
亢一娜
赵世贤
孙红刚
杜一昊
尚心莲
司瑶晨
夏淼
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract

The invention belongs to the field of refractory materials, and relates to a magnesium aluminate spinel-silicon carbide-aluminum composite refractory material. The related magnesia-alumina spinel-silicon carbide-aluminum composite refractory material comprises aggregate and a matrix; the aggregate is fused magnesia-alumina spinel particles and sintered magnesia-alumina spinel particles, and the adding amount of the fused magnesia-alumina spinel particles and the sintered magnesia-alumina spinel particles is 50 to 70 percent of the total amount of the raw materials; the matrix is silicon carbide, aluminum oxide and magnesium oxide; the matrix is also added with coated metal aluminum powder, and the adding proportion is 2-8% of the total mass of the raw materials; and uniformly mixing the aggregate, the matrix and the bonding agent, then carrying out compression molding, drying, and then firing under a carbon-embedded atmosphere to obtain the magnesia-alumina spinel-silicon carbide-aluminum composite refractory material. The invention improves the high-temperature mechanical strength, the thermal shock stability and the coal cinder erosion resistance of the product.

Description

Magnesium aluminate spinel-silicon carbide-aluminum composite refractory material
Technical Field
The invention belongs to the field of refractory materials, and mainly relates to a magnesium aluminate spinel-silicon carbide-aluminum composite refractory material.
Background
The coal water slurry gasification technology is a mainstream coal gasification technology widely applied at home and abroad in recent years; a water-coal-slurry gasification furnace is an important device in the field of coal gasification, and takes coal and water as main raw materials to prepare gaseous H by utilizing the combustion of the water-coal-slurry in a high-temperature and high-pressure environment2、CO、CO2Advanced equipment for equalizing chemical raw materials; the operation temperature of the coal water slurry gasification furnace is high, the working environment is severe, and under the high temperature environment and higher pressure in the furnace, the lining material is seriously abraded and peeled off due to continuous scouring of gas, liquid and solid phase substances, so that the normal operation of the coal water slurry gasification furnace is restricted, and the high-temperature mechanical property of the coal water slurry gasification furnace needs to be considered as an important performance index when the lining material of the fire facing surface of the coal water slurry gasification furnace is selected; at present, the coal water slurry gasification furnace generally adopts a high-chromium refractory material with excellent high-temperature performance, the high-temperature mechanical property is high, the cinder erosion resistance is excellent, and the Cr is2O3With Al2O3Has similar crystal structure and Al at certain temperature2O3And Cr2O3Better crystallization is generated, continuous aluminum-chromium solid solution is generated, the bonding strength of the material matrix is increased, and the high-temperature mechanical property is improved, but because the service life is shorter and Cr is generated in the reaction process6+Causing serious pollution to the environment.
Aiming at the problems of high-chromium bricks, the chromium-free refractory material for the coal water slurry gasification furnace becomes a hot spot for research and development of refractory materials in recent years; spinel-based refractory materials have been widely used in the fields of ladle linings, cement kilns, glass kilns, black liquor gasification and the like due to their excellent high-temperature strength and high erosion resistance; in addition, the results associated with alumina-based, magnesia-based and silicon carbide-based refractories, including Al, have been reported in sequence2O3-CaO、Al2O3-SiC-C, MgO-MA, non-oxide bonded SiC, and the like, but none of these materials show good resistance to cinder erosion in special coal gasification environments. Patent application 201911265641.9The magnesia-alumina spinel-silicon carbide composite refractory material is prepared by using magnesia-alumina spinel particles as aggregate and silicon carbide, magnesia-alumina spinel, alumina, magnesia and simple substance silicon as matrixes, compacting, forming and then sintering at 1350-1750 ℃ in a carbon-buried atmosphere or a nitrogen atmosphere. The magnesium aluminate spinel-silicon carbide composite refractory material has excellent erosion resistance, but has poor high-temperature mechanical property (the high-temperature breaking strength under the condition of carbon burying at 1650 ℃ is about 1-3 MPa), and the material is easy to abrade and peel under the severe working environment of a coal water slurry gasification furnace, so that the excellent coal slag permeation and erosion resistance cannot be embodied. The main reasons for the low high-temperature mechanical strength are: under the carbon-buried atmosphere or nitrogen atmosphere, the silicon carbide fine powder in the material matrix can still be partially oxidized to generate SiO2And a low-melting-point glass phase is formed, and in the high-temperature use process, the glass phase is converted from a solid state into a liquid state, so that the stability of the material matrix structure is damaged, and the high-temperature mechanical strength of the material matrix is far lower than the normal-temperature mechanical strength.
Disclosure of Invention
The invention aims to provide a magnesium aluminate spinel-silicon carbide-aluminum composite refractory material which can improve the high-temperature mechanical property of the material on the premise of not reducing the slag corrosion resistance of the material.
The invention adopts the following technical scheme for achieving the purpose:
1. a magnesia-alumina spinel-silicon carbide-aluminum composite refractory material comprises raw materials of aggregate and matrix; the method is characterized in that: the aggregate is fused magnesia-alumina spinel particles and sintered magnesia-alumina spinel particles, and the adding amount of the fused magnesia-alumina spinel particles and the sintered magnesia-alumina spinel particles is 50 to 70 percent of the total amount of the raw materials; the matrix is silicon carbide, aluminum oxide and magnesium oxide, wherein the adding proportion of the silicon carbide is 25-40% of the total mass of the raw materials, the adding proportion of the aluminum oxide is 2-8% of the total mass of the raw materials, and the adding proportion of the magnesium oxide is 2-8% of the total mass of the raw materials; the substrate is also added with coated metal aluminum powder with the granularity range of 10-45 mu m, and the adding proportion is 2-8% of the total mass of the raw materials; the aggregate, the matrix and the bonding agent are uniformly mixed and then are subjected to mechanical forming, and the mixture is dried and then is subjected to secondary sinteringFiring at the highest temperature of 1400-1650 ℃ under a carbon-embedding atmosphere to obtain the magnesia-alumina spinel-silicon carbide-aluminum composite refractory material taking magnesia-alumina spinel as a main crystal phase and silicon carbide as a secondary crystal phase; al (Al)2O3The sum of the mass fractions of + MgO + SiC is greater than 97%, wherein Al2O352.5 to 65.5 percent of mass fraction, 11.5 to 21.5 percent of MgO mass fraction and 20.5 to 33.4 percent of SiC mass fraction.
The purity of the electric melting magnesia-alumina spinel particles and the sintered magnesia-alumina spinel particles is highw(Al2O3+ MgO) greater than or equal to 99.0%, wherein Al2O3The mass fraction of the particles is 75-90%, and the particle size range is 0-3 mm; the magnesium aluminate spinel is Al2O3MgAl formed at high temperature with MgO2O4And solid solution thereof, so the magnesia-alumina spinel has wider chemical composition, the magnesia-alumina spinel with a more compact structure can be prepared by adopting an electric melting method, and the magnesia-alumina spinel aggregate prepared by a sintering method has rough surface and high reaction activity; requires Al2O3The total mass fraction of the MgO is more than or equal to 99.0 percent, and the high-purity magnesia-alumina spinel has more excellent slag corrosion resistance; requires Al in magnesium aluminate spinel2O3The mass fraction is more than or equal to 75 percent, mainly because the corrosion resistance of the aluminum-rich spinel to the meta-acid slag is strong; the particle size of the magnesium aluminate spinel is required to be 0-3 mm, the silicon carbide fine powder can be better filled between magnesium aluminate spinel particle frameworks mainly from the aspects of particle composition and sintering activity, the strength of the material can be effectively improved, and if the particle size of spinel powder is too small, the activity is too high, the product shrinkage is large during sintering, and the yield is low.
The silicon carbide is sintered silicon carbide fine powder prepared by a sintering method, the purity w (SiC) is more than or equal to 98 percent, the granularity range is 20-100 mu m, the high-temperature performance is excellent, and the coal cinder erosion resistance is good; the purity requirement of the sintered silicon carbide fine powder is as followsw(SiC) ≥ 98% because if the purity of silicon carbide is low, SiO is easily formed at high temperature2、Fe2O3、Na2O、K2O and the like are easy to form low-melting-point substances at high temperature, and the high-temperature mechanical property and slag resistance of the refractory material are reduced. The granularity of the sintered silicon carbide fine powder is required to be 20-100 mu m, and carbonThe silicon carbide has a certain particle size range, on one hand, the compactness and the bonding performance of the product are improved, and on the other hand, the too large particle size of the silicon carbide can cause difficult molding of a material green body and increase of the sintering difficulty.
The metal aluminum powder subjected to coating treatment adopts compact Al after being coated by aluminum sol2O3The spherical metal aluminum powder of the shell has a particle sphericity of 0.8-1; the surface coating treatment method of the metal aluminum powder comprises the following steps:
(1) industrial aluminium sol (chemical molecular formula is Al)2(OH)n·Cl6-n) Adding alumina nano powder with the particle size of 10-20 nm into a carrier, wherein the mass ratio of the alumina nano powder to the aluminum sol is 1:10, and performing ultrasonic dispersion for 5-10 min to obtain the aluminum sol with the alumina nano powder uniformly distributed;
(2) adding metal aluminum powder with the particle size of 5-32 mu m into the aluminum sol containing the alumina nano powder obtained in the step (1), wherein the mass ratio of the metal aluminum powder to the sol is 1:5, performing ultrasonic dispersion for 10-15 min, performing suction filtration to obtain metal aluminum powder with the surface uniformly coated by the aluminum sol containing the active alumina nano powder, and drying at 100-120 ℃ for 24-48 h to obtain metal aluminum powder with a compact alumina shell; the sphericity of the particles is required to have a certain range, which is mainly to increase the fluidity of the metal aluminum powder among the matrixes and ensure that the metal aluminum powder is uniformly dispersed among the matrixes; on the other hand, the coating effect of the metal aluminum powder is good, and the Al shell is more uniform in spherical shape compared with flaky or irregular shape2O3The thickness of each part is uniform, the internal and external acting force is relatively uniform at high temperature, and the structure weak position is not easy to exist.
The alumina is one of plate corundum fine powder or active alumina micro powder, and Al2O3The mass fraction of the active alumina is more than or equal to 98 percent, wherein the granularity range of the plate-shaped corundum fine powder is 43-74 mu m, and the granularity range of the active alumina micro powder is D50= 2-5 μm, the main purpose of adding the tabular corundum fine powder or activated alumina fine powder is to promote sintering of the product at high temperature and to improve the normal temperature and high temperature strength of the refractory material, and on the other hand, to react with MgO in the matrix at high temperature to formIn-situ magnesium aluminate spinel.
The magnesium oxide is light-burned magnesium oxide powder, the mass fraction of MgO is more than or equal to 98 percent, and the granularity range is D50The fine powder or micro powder of spinel prepared by an electric melting method or a sintering method has lower activity, and in order to improve the mechanical strength and the slag resistance of the product, the aluminum oxide and the magnesium oxide are added to generate the in-situ magnesia-alumina spinel which is more tightly combined with the matrix and has higher activity at high temperature.
The binding agent is a resin organic matter binding agent and is one of amino water-soluble resin and phenolic resin; in the forming process, the resin is beneficial to the bonding between the aggregate and the matrix, so that the formed material is more compact and has certain strength, the resin is lost at high temperature to form carbon residue, and the carbon residue has a fiber structure of carbon nanotubes or carbon fibers, is preferentially oxidized by SiC and plays a role in delaying the oxidation of SiC.
The invention provides a magnesia-alumina spinel-silicon carbide-aluminum composite refractory material which is sintered in a carbon-buried atmosphere, and when the sintering temperature is lower than 1500 ℃, SiC fine powder or micro powder in a matrix and O in the air2The reaction is carried out, SiC is weakly oxidized to generate SiO2SiO of the2Reacting with impurities in the matrix to generate a low-melting-point glass phase; when the temperature is higher than 1500 ℃, the SiC undergoes inert oxidation and active oxidation simultaneously, and the product is liquid phase SiO2And gas phase SiO, the content of liquid phase in the matrix is gradually increased, and more low-melting-point glass phase is formed. When the magnesium aluminate spinel-silicon carbide composite refractory material is prepared, metal aluminum powder is usually added into a matrix as an antioxidant, and the aluminum powder is preferentially oxidized to obviously delay the oxidation of SiC; however, the metal aluminum powder has very active property, and can react with water violently at room temperature to 100 ℃ to generate H2And release a large amount of heat, which adversely affects the internal structure of the green body of the refractory product; the metal aluminum powder is directly added into the refractory product, so that the use of a material bonding agent is limited, and on the other hand, the reaction of the metal aluminum powder and water vapor in the air in the process of standing the green product at normal temperature causes the product to generate a serious pulverization phenomenon, so that the normal-temperature storage of the green product becomes a difficult problem; in the process of high-temperature sintering,the reaction process and the reaction form of the metal aluminum powder are not controllable, and whether the metal aluminum powder is added or not has limited influence on the high-temperature mechanical property of the material.
The invention adds the spherical metal aluminum powder with compact active alumina shell after coating treatment into the substrate, when the firing temperature is lower than 1400 ℃, the spherical inner metal aluminum powder is in a stable state, when SiC is oxidized and generated, SiO2With Al2O3The reaction generates mullite phase with higher melting point, and destroys the shell structure of the metal aluminum powder, the internal metal aluminum is diffused into the material in the form of gas phase aluminum or aluminum oxygen compound, and is mixed with O in the atmosphere2CO or N2Reacts quickly to generate Al with higher activity2O3、Al4C3Or AlN, followed by further reaction with SiO2MgO, etc. form a mullite phase (3 Al) having a high melting point2O3·2SiO2Melting point 1900 deg.C), corundum (Al)2O3Melting point 2000-2030 deg.C and trace amount of cordierite phase (Mg)2Al4Si5O18Melting point 1460 deg.C) and, reduction of SiO in the matrix2A predominantly low-melting glass phase (melting point below 1300 c) is formed. Part of mullite, cordierite or corundum products are in a random whisker shape, so that the expansion of cracks in the material can be prevented, and the high-temperature mechanical property of the magnesia-alumina spinel-silicon carbide refractory material can be improved; compared with the prior art, the invention simultaneously improves the high-temperature mechanical strength, the thermal shock stability and the coal cinder erosion resistance of the product, and ensures the normal use of the coal water slurry gasification furnace at 1300-1500 ℃; the invention provides a magnesium aluminate spinel-silicon carbide-aluminum composite refractory material which has the apparent porosity of 15-23% and the volume density of 2.63 g/cm3～2.87g/cm3And the high-temperature breaking strength (1400 ℃ carbon buried for 30 min) is 6-18 MPa.
Detailed Description
The invention is illustrated by the examples given, but is not to be construed as being in any way limited thereto.
Example 1:
respectively weighing the chemical compositionsw(SiC) =98%, and sintered silicon carbide particles having a particle size of 40 to 100 μm30kg of powder with chemical composition ofw(Al2O3) =98% particle size D503kg of active alumina micropowder with the chemical composition of 2-5 mu mw(MgO) =98.2%, particle size D503kg of light-burned magnesia powder with the particle size of 4-8 mu m and 2kg of coated metal aluminum powder with the particle size of 10-20 mu m and the sphericity of 0.92 are put into a ball mill together and premixed for 1h to prepare substrate fine powder; respectively taking the purityw(Al2O3+ MgO) =99.1% of Al2O325kg of electric melting magnesia-alumina spinel particles with the mass fraction of 78 percent and the particle size range of 1-3 mm,w(Al2O3+ MgO) =99.1% of Al2O3The preparation method comprises the following steps of adding 37kg of sintered magnesia-alumina spinel particles with the mass percentage of 78% and the particle size range of 0-1 mm into a roller mill, uniformly mixing, adding about 2kg of amino water-soluble resin into the particles, stirring, adding premixed matrix fine powder, fully mixing, ageing for 24 hours, forming a green body with the particle size of 150mm × 25mm × 25mm in a steel mould at 110MPa, drying for 12 hours at 180 ℃, placing the green body into a corundum sagger filled with 100-mesh graphite powder, sealing a sample and graphite in the sagger, and sintering in a resistance furnace at 1450 ℃ to obtain the magnesia-alumina spinel-silicon carbide composite refractory product, wherein the apparent porosity of the magnesia-alumina spinel-silicon carbide composite refractory product is 21.8%, and the volume density is 2.69g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 7 MPa.
Example 2:
respectively weighing the chemical compositionsw(SiC) =98.8%, 32kg of sintered silicon carbide fine powder with the particle size of 40-100 mu m and chemical compositionw(Al2O3) =98.4% particle size D504kg of active alumina micropowder with the chemical composition of 2-5 mu mw(MgO) =98.8%, particle size D50Putting 4g of light-burned magnesia powder with the particle size of 4-8 mu m and 3kg of coated metal aluminum powder with the particle size of 10-20 mu m and the sphericity of 0.93 into a ball mill for premixing for 1h to prepare substrate fine powder; respectively taking the purityw(Al2O3+ MgO) =99.8%, wherein Al2O328kg of fused magnesia-alumina spinel with the mass fraction of 78.3 percent and the granularity of 1-3 mm,w(Al2O3+ MgO) =99.8%, wherein Al2O3The preparation method comprises the following steps of adding 29kg of sintered magnesia-alumina spinel particles with the mass fraction of 78.3% and the particle size range of 0-1 mm into a roller mill mixer, uniformly mixing, adding about 4kg of phenolic resin into the particles, stirring, adding premixed matrix fine powder, fully mixing, ageing for 24 hours, forming a green body with the particle size of 150mm × 25mm × 25mm in a steel mold under the pressure of 110MPa, drying at 180 ℃ for 12 hours, placing the green body into a corundum sagger filled with 100-mesh graphite powder, sealing a sample and the graphite in the sagger, and sintering at 1500 ℃ in a resistance furnace to obtain the magnesia-alumina spinel-silicon carbide composite refractory product, wherein the magnesia-alumina spinel-silicon carbide composite refractory product has the porosity of 19.3% and the volume density of 2.64g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 12 MPa.
Example 3:
respectively weighing the chemical compositionsw(SiC) =98.4%, 29kg of sintered silicon carbide fine powder with the particle size of 40-100 mu m and chemical compositionw(Al2O3) =98.6% particle size D506kg of alumina micropowder with the chemical composition of 2-5 mu mw(MgO) =98.4%, particle size D50Putting 6kg of light-burned magnesia powder with the particle size of 4-8 mu m and 5kg of coated metal aluminum powder with the particle size of 10-20 mu m and the sphericity of 0.88 into a ball mill for premixing for 1h to prepare substrate fine powder; respectively taking the purityw(Al2O3+ MgO) =99.1% of Al2O324kg of fused magnesia-alumina spinel with the mass fraction of 80.5 percent and the granularity range of 1-3 mm and the purityw(Al2O3+ MgO) =99.1% of Al2O3Adding 30kg of sintered magnesia alumina spinel particles with the mass fraction of 80.5% and the particle size range of 0-1 mm into a roller mill, uniformly mixing, adding about 6kg of phenolic resin into the particles, stirring, adding premixed matrix fine powder, fully mixing, ageing for 24 hours, forming a green body with the particle size of 150mm × 25mm × 25mm in a steel mould at 110MPa, drying at 180 ℃ for 12 hours, placing the green body into a corundum sagger filled with 100-mesh graphite powder, sealing a sample and graphite in the sagger, and sintering in a resistance furnace at 1550 ℃ to obtain the magnesia alumina spinel-silicon carbide composite refractory material productThe apparent porosity of the composite refractory product is 20.9 percent, and the volume density is 2.69g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 11 MPa.
Example 4:
respectively weighing the chemical compositionsw(SiC) =98.7%, 28kg of sintered silicon carbide fine powder with the particle size of 40-100 mu m and chemical compositionw(Al2O3) =98.3%, 5kg of tabular corundum fine powder with the particle size of 43-74 μm and the chemical composition of the tabular corundum fine powderw(MgO) =98.5%, particle size D50Putting 5kg of light-burned magnesia powder with the particle size of 4-8 mu m and 4kg of coated metal aluminum powder with the particle size of 10-20 mu m and the sphericity of 0.94 into a ball mill for premixing for 1h to prepare substrate fine powder; respectively taking the purityw(Al2O3+ MgO) =99.7% of Al2O320kg of fused magnesia-alumina spinel with the mass fraction of 78.7 percent and the granularity of 1-3 mm and the purityw(Al2O3+ MgO) =99.7% of Al2O3Adding 38kg of sintered magnesia alumina spinel particles with the mass fraction of 78.7% and the particle size range of 0-1 mm into a roller mill mixer, uniformly mixing, adding about 3kg of phenolic resin into the particles, stirring, adding premixed matrix fine powder, fully mixing, ageing for 24 hours, forming a green body with the particle size of 150mm × 25mm × 25mm in a steel mould at 110MPa, drying at 180 ℃ for 12 hours, placing the green body into a corundum sagger filled with 100-mesh graphite powder, sealing a sample and graphite in the sagger, and sintering at 1650 ℃ in a resistance furnace to obtain the magnesia alumina spinel-silicon carbide composite refractory product, wherein the apparent porosity of the magnesia alumina spinel-silicon carbide composite refractory product is 15.9%, and the volume density of the magnesia alumina spinel-silicon carbide composite refractory product is 2.83g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 16 MPa.
Example 5:
respectively weighing the chemical compositionsw(SiC) =98.4%, 35kg of sintered silicon carbide fine powder with the particle size of 40-100 mu m and chemical compositionw(Al2O3) =98.2% particle size D502kg of active alumina micropowder with the chemical composition of 2-5 mu mw(MgO) =98.6%, particle size D502kg of light-burned magnesia powder with the grain size of 10-20 mu m and the sphericity of 0.956kg of processed metal aluminum powder is put into a ball mill together for premixing for 1h to prepare matrix fine powder; respectively taking the purityw(Al2O3+ MgO) =99.6% of Al in the alloy2O330kg of fused magnesia-alumina spinel with the mass fraction of 86.1 percent and the granularity range of 1-3 mm is takenw(Al2O3+ MgO) =99.6% of Al in the alloy2O3Adding 25kg of sintered magnesia alumina spinel particles with the mass fraction of 86.1 percent and the particle size range of 0-1 mm into a roller mill mixer, uniformly mixing, adding about 6kg of phenolic resin into the particles, stirring, adding premixed matrix fine powder, fully mixing, ageing for 24 hours, forming a green body with the particle size of 150mm × 25mm × 25mm in a steel mould at 110MPa, drying at 180 ℃ for 12 hours, placing the green body into a corundum sagger filled with 100-mesh graphite powder, sealing a sample and graphite in the sagger, and sintering at 1450 ℃ in a resistance furnace to obtain the magnesia alumina spinel-silicon carbide composite refractory product, wherein the magnesia alumina spinel-silicon carbide composite refractory product has the apparent porosity of 19.3 percent and the volume density of 2.74g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 12 MPa.
Example 6:
respectively weighing the chemical compositionsw(SiC) =99.2%, 25kg of sintered silicon carbide fine powder with the particle size of 40-100 mu m, and the chemical composition of the sintered silicon carbide fine powder isw(Al2O3) =99.2%, 4kg of tabular corundum fine powder with a particle size of 43-74 μm and a chemical composition ofw(MgO) =98%, particle size D50Putting 4kg of light-burned magnesia powder with the particle size of 4-8 mu m and 4kg of coated metal aluminum powder with the particle size of 10-20 mu m and the sphericity of 0.90 into a ball mill for premixing for 1h to prepare substrate fine powder; respectively taking the purityw(Al2O3+ MgO) =99.1% of Al2O335kg of fused magnesia-alumina spinel with the mass fraction of 86.2 percent and the granularity range of 1-3 mm and the purityw(Al2O3+ MgO) =99.1% of Al2O3Adding 28kg of sintered magnesia-alumina spinel particles with the mass fraction of 86.2% and the particle size range of 0-1 mm into a roller type sand mixer, and uniformly mixing; adding about 4kg of phenolic resin into the particles, stirring, adding the premixed matrix fine powder, fully mixing, and ageing for 24 hours; in steelForming a green body with the thickness of 150mm × 25mm × 25mm at 110MPa in a mold, drying the green body for 12h at 180 ℃, placing the green body in a corundum sagger filled with 100-mesh graphite powder, sealing a sample and graphite in the sagger, and firing the green body in a resistance furnace at 1600 ℃ to obtain the magnesia-alumina spinel-silicon carbide composite refractory material product, wherein the apparent porosity of the magnesia-alumina spinel-silicon carbide composite refractory material product is 22.7%, and the volume density of the magnesia-alumina spinel-silicon carbide composite refractory material product is 2.80g/cm-3And the high-temperature breaking strength (1400 ℃ for 30min, carbon burying) is 12 MPa.

Claims (7)

1. A magnesia-alumina spinel-silicon carbide-aluminum composite refractory material comprises raw materials of aggregate and matrix; the method is characterized in that: the aggregate is fused magnesia-alumina spinel particles and sintered magnesia-alumina spinel particles, and the adding amount of the fused magnesia-alumina spinel particles and the sintered magnesia-alumina spinel particles is 50 to 70 percent of the total amount of the raw materials; the matrix is silicon carbide, aluminum oxide and magnesium oxide, wherein the adding proportion of the silicon carbide is 25-40% of the total mass of the raw materials, the adding proportion of the aluminum oxide is 2-8% of the total mass of the raw materials, and the adding proportion of the magnesium oxide is 2-8% of the total mass of the raw materials; the substrate is also added with coated metal aluminum powder with the granularity range of 10-45 mu m, and the adding proportion is 2-8% of the total mass of the raw materials; the aggregate, the matrix and the bonding agent are uniformly mixed and then subjected to mechanical pressing forming, and after drying, the mixture is sintered at the highest temperature of 1400-1650 ℃ under the carbon-embedded atmosphere to obtain the magnesia-alumina spinel-silicon carbide-aluminum composite refractory material taking magnesia-alumina spinel as a main crystal phase and silicon carbide as a secondary crystal phase; al (Al)2O3The sum of the mass fractions of + MgO + SiC is greater than 97%, wherein Al2O352.5 to 65.5 percent of mass fraction, 11.5 to 21.5 percent of MgO mass fraction and 20.5 to 33.4 percent of SiC mass fraction.
2. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the magnesia-alumina spinel particles are an electric melting or sintering raw material, the particle size range is 0-3 mm,w(Al2O3+ MgO) greater than or equal to 99.0%, wherein Al2O3The mass fraction of the fused magnesia-alumina spinel is 75-90%, and the adding proportion of the fused magnesia-alumina spinel is the total mass of the raw materialsThe amount of the sintered magnesia-alumina spinel is 20 to 35 percent, and the adding proportion of the sintered magnesia-alumina spinel is 25 to 40 percent of the total mass of the raw materials.
3. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the silicon carbide fine powder or micro powder is prepared by adopting a sintering method, and the purity requirement of the silicon carbide iswThe (SiC) is more than or equal to 98 percent, and the granularity is required to be 20-100 mu m.
4. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the coated metal aluminum powder is spherical metal aluminum powder coated on the surface of alumina sol, the spherical granularity is 0.8-1, and after the coating treatment of the surface of the alumina sol, the outer surface of the spherical metal aluminum powder is coated with a layer of compact Al2O3A housing.
5. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the alumina is one of plate corundum fine powder or active alumina micro powder, and Al2O3The mass fraction of the active alumina is more than or equal to 98 percent, wherein the granularity range of the plate-shaped corundum fine powder is 43-74 mu m, and the granularity range of the active alumina micro powder is D50=2～5μm。
6. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the magnesium oxide is light-burned magnesium oxide powder, the mass fraction of MgO is more than or equal to 98 percent, and the granularity range is D50=4μm～8μm。
7. The magnesium aluminate spinel-silicon carbide-aluminum composite refractory material of claim 1, wherein: the binder is a resin organic matter binder and is one of amino water-soluble resin and phenolic resin.
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