CN107235732B - Mullite coated refractory material - Google Patents
Mullite coated refractory material Download PDFInfo
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- CN107235732B CN107235732B CN201710265227.2A CN201710265227A CN107235732B CN 107235732 B CN107235732 B CN 107235732B CN 201710265227 A CN201710265227 A CN 201710265227A CN 107235732 B CN107235732 B CN 107235732B
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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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
Abstract
The invention discloses a mullite-wrapped refractory material, which comprises α -alumina, spodumene, zirconite, sodium silicate, water, high-alumina and mullite, and also discloses a preparation method of the mullite-wrapped refractory material.
Description
Technical Field
The invention relates to a refractory material, in particular to a mullite coated refractory material and a preparation method thereof.
Background
At present, mullite products appearing in the market mainly comprise mullite-cordierite products, corundum-mullite products and silicon carbide-mullite products. The mullite-cordierite product has low thermal expansion, can be used for quick firing, but has higher pores and lower use temperature; the corundum-mullite product has higher strength and good chemical stability, but has poor thermal shock resistance; the silicon carbide-mullite product has the advantages of high strength and good thermal shock, but is easy to oxidize in the using process, the service life is easy to influence, and the silicon carbide material is more expensive compared with mullite.
The high-alumina bauxite can also be used for manufacturing mullite refractory materials, the price is not high, but the mullite brick produced by adopting the raw materials generally has the defect of extremely poor anti-reduction performance; the main reason is that the high-alumina bauxite has high iron content and can be used as a catalyst after being contacted with a reducing atmosphere in the working process, carbon is deposited in the brick body, and the brick body is damaged, so that the brick cannot be used for a dry quenching annular air duct and a cooling chamber.
The mullite brick made of the high-purity mullite raw material can greatly improve the reduction resistance of the material, but the material is too expensive to be widely applied.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the problem that the existing refractory material cannot give consideration to thermal expansion performance, use temperature, strength, chemical stability, thermal shock resistance, oxidation resistance and price.
The technical scheme includes that the mullite coated refractory material comprises α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite.
Preferably, the grain size of the bauxite and the mullite cannot exceed 5 millimeters.
The α -aluminum oxide, spodumene, zirconite, sodium silicate, water, alumina and mullite are optimally mixed according to the proportion of 1-5 parts of α -aluminum oxide, 3-8 parts of spodumene, 3-8 parts of zirconite, 1-7 parts of sodium silicate, 20-30 parts of water, 37-75 parts of high-alumina and 40-70 parts of mullite.
The α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are optimally mixed according to the proportion of 3 parts of α -alumina, 6 parts of spodumene, 6 parts of zirconite, 4 parts of sodium silicate, 25 parts of water, 56 parts of high alumina and 55 parts of mullite.
Preferably, the aluminum content of the mullite is at least 60 percent, namely at least M60 mullite is adopted.
Preferably, the bauxite is high bauxite, and the aluminum content is 80-85%.
A preparation method of a mullite coated refractory material comprises the following steps:
1) mixing α -alumina, spodumene, zirconite, sodium silicate and water, stirring, and putting into a ball mill for ball milling for 1-3 hours to prepare slurry;
2) mixing the slurry prepared in the step 1) with alumina and mullite;
3) drying the mixture obtained in the step 2) to obtain a wrapping material.
Preferably, the mixing ratio of the alumina and the mullite in the step 2) to the slurry is 7: 3.
Optimally, in the step 2), the bauxite and the mullite are mixed and then added into the slurry to be mixed and ground for 15-25 min, so that the slurry is completely wrapped on the surfaces of the particles.
Preferably, the drying in the step 3) is drying for 1-3 hours at the temperature of 100-110 ℃.
The principle is that the mullite-wrapped refractory material adopts a raw material wrapping method in the preparation process to prevent iron in the raw material from contacting with a reducing atmosphere, the wrapping material in the material can generate a high-temperature viscous liquid phase during high-temperature sintering, the liquid phase can fill pores in the material to reduce the amount of the pores in the material, particularly the content of through pores, and can also form a film protection on the particle part of the material in the working process to prevent the iron in the material from contacting with the reducing atmosphere to prevent the 'iron' in the material from being reduced to achieve the purpose of reducing resistance, meanwhile, the high-temperature viscous liquid phase can fully fill the pores between the particles, particularly the through pores, reduce the porosity of the material, improve the sintering compactness of the material, and improve the bonding strength of the material, wherein α -alumina in the raw material can be wrapped with SiO2And free SiO produced by sintering zircon2A small amount of mullite grains are formed during firing to fill the gaps between the aggregates, which results in a further increase in the strength of the material. The spodumene in the wrapper has little expansion during firing and has no influence on various properties of the material. And zircon in Al2O3If the zirconia exists, the zirconia generated by decomposition partially forms a solid solution with the zirconia, fills gaps among particles, and improves compactness.
Active α -alumina micropowder and SiO2The micro powder is added into the matrix material, and the aim is that a small amount of micro powder is decomposed to form mullite and free SiO in the firing process2The added α -alumina micro powder can generate secondary mullite reaction with the alumina micro powder, the formed secondary mullite is in fiber or columnar mullite staggered distribution, and the distribution ensures that the material has good thermal shock stability and higher strength.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) adopt α -aluminium oxide to improve the intensity of wrapping material, adopt spodumene to improve the thermal stability of wrapping material, adopt zircon to make the wrapping material can have adiabatic effect, add sodium silicate and improve wrapping material acid resistance and heat resistance as the adhesive, bauxite and sodium silicate cooperation further improve the alkali resistance and the plasticity of wrapping material.
2) The wrapping material can generate a high-temperature viscous liquid phase during high-temperature sintering, and the liquid phase can fill pores in the material, so that the pore amount in the material is reduced, and particularly the content of through pores is reduced; meanwhile, a film can be formed on the particle part of the material for protection in the working process, so that the contact of iron in the material and the reducing atmosphere is prevented, the reduction of the 'iron' in the material is prevented, and the purpose of reducing resistance is achieved.
Detailed Description
The present invention is further explained below.
Example 1
A mullite-coated refractory material comprises α -alumina, spodumene, zircon, sodium silicate, water, alumina and mullite.
The grain size of the high bauxite and the mullite cannot exceed 5 millimeters.
The α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are mixed according to the proportion of 1 part of α -alumina, 3 parts of spodumene, 3 parts of zirconite, 1 part of sodium silicate, 20 parts of water, 37 parts of alumina and 40 parts of mullite.
The aluminum content of the mullite is 60 percent, namely M60 mullite is adopted.
The bauxite is high-alumina bauxite, and the aluminum content is 80%.
Example 2
A mullite-coated refractory material comprises α -alumina, spodumene, zircon, sodium silicate, water, alumina and mullite.
The grain size of the high bauxite and the mullite cannot exceed 5 millimeters.
The α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are mixed according to the proportion of 5 parts of α -alumina, 8 parts of spodumene, 8 parts of zirconite, 7 parts of sodium silicate, 30 parts of water, 75 parts of alumina and 70 parts of mullite.
The aluminum content of the mullite is 60 percent, namely M60 mullite is adopted.
The bauxite is high-alumina bauxite, and the aluminum content is 80%.
Example 3
A mullite-coated refractory material comprises α -alumina, spodumene, zircon, sodium silicate, water, alumina and mullite.
The grain size of the high bauxite and the mullite cannot exceed 5 millimeters.
The α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are mixed in the proportion of 3 parts of α -alumina, 6 parts of spodumene, 6 parts of zirconite, 4 parts of sodium silicate, 25 parts of water, 56 parts of high alumina and 55 parts of mullite.
The aluminum content of the mullite is 60 percent, namely M60 mullite is adopted.
The bauxite is high-alumina bauxite, and the aluminum content is 80%.
Example 4
The mullite-wrapped refractory material adopts a raw material wrapping method in the preparation process, and aims to prevent iron in the raw material from contacting with a reducing atmosphere, the wrapping material in the material can generate a high-temperature viscous liquid phase during high-temperature sintering, the liquid phase can fill pores in the material, reduce the amount of the pores in the material, particularly the content of through pores, can form a film protection on the particle part of the material during the working process, prevent the iron in the material from contacting with the reducing atmosphere, prevent the 'iron' in the material from being reduced, and play a role in resisting reduction, and simultaneously the high-temperature viscous liquid phase can fully fill the pores between the particles, particularly the through pores, reduce the porosity of the material, improve the sintering compactness of the material, and improve the bonding strength of the material, wherein α -alumina in the raw material can be wrapped with SiO2And free SiO produced by sintering zircon2A small amount of mullite grains are formed during firing to fill the gaps between the aggregates, which results in a further increase in the strength of the material. The spodumene in the wrapper has little expansion during firing and has no influence on various properties of the material. And zircon in Al2O3If the zirconia exists, the zirconia generated by decomposition partially forms a solid solution with the zirconia, fills gaps among particles, and improves compactness.
Example 5
A preparation method of a mullite coated refractory material comprises the following steps:
1) mixing α -alumina, spodumene, zirconite, sodium silicate and water, stirring, and putting into a ball mill for ball milling for 1-3 hours to prepare slurry;
2) mixing the slurry prepared in the step 1) with alumina and mullite;
3) drying the mixture obtained in the step 2) to obtain a wrapping material.
The mixing ratio of the alumina and mullite in the step 2) to the slurry is 7: 3.
And 2) mixing the alumina and the mullite in the step 2), adding the slurry, and carrying out mixed grinding for 15-25 min to enable the slurry to be completely wrapped on the surfaces of the particles.
The drying in the step 3) is drying for 1-3 hours at the temperature of 100-110 ℃.
And (3) after the preparation, wrapping the obtained wrapping material outside the blank body, and sintering at 1250-1450 ℃ to obtain the formed brick.
Active α -alumina micropowder and SiO2The micro powder is added into the matrix material, and the aim is that a small amount of micro powder is decomposed to form mullite and free SiO in the firing process2The added α -alumina micro powder can generate secondary mullite reaction with the alumina micro powder, the formed secondary mullite is in fiber or columnar mullite staggered distribution, and the distribution ensures that the material has good thermal shock stability and higher strength.
The present invention provides a mullite-wrapped refractory material and a method for preparing the same, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the present invention, and these improvements and decorations should also be regarded as the protection scope of the present invention, and each component not explicitly described in the embodiment can be implemented by the existing technology.
Claims (6)
1. A preparation method of a mullite coated refractory material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing α -alumina, spodumene, zirconite, sodium silicate and water, stirring, and putting into a ball mill for ball milling for 1-3 hours to prepare slurry;
2) mixing the slurry prepared in the step 1) with alumina and mullite;
3) drying the mixture obtained in the step 2) to obtain a wrapping material;
the α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are prepared from 1-5 parts of α -alumina, 3-8 parts of spodumene, 3-8 parts of zirconite, 1-7 parts of sodium silicate, 20-30 parts of water, 37-75 parts of high-alumina and 40-70 parts of mullite;
the grain size of the high bauxite and the mullite cannot exceed 5 mm;
the mixing ratio of the alumina and mullite in the step 2) to the slurry is 7: 3.
2. The method for preparing a mullite-encased refractory according to claim 1, wherein: the aluminum content of the mullite is at least 60 percent, namely at least M60 mullite is adopted.
3. The method for preparing a mullite-encased refractory according to claim 1, wherein: the bauxite is high-alumina bauxite, and the aluminum content is 80-85%.
4. The method for preparing the mullite-wrapped refractory according to claim 1, wherein the α -alumina, spodumene, zirconite, sodium silicate, water, alumina and mullite are mixed in the ratio of 3 parts of α -alumina, 6 parts of spodumene, 6 parts of zirconite, 4 parts of sodium silicate, 25 parts of water, 56 parts of bauxite and 55 parts of mullite.
5. The method for preparing a mullite-encased refractory according to claim 1, wherein: and 2) mixing the alumina and the mullite in the step 2), adding the slurry, and carrying out mixed grinding for 15-25 min to enable the slurry to be completely wrapped on the surfaces of the particles.
6. The method for preparing a mullite-encased refractory according to claim 1, wherein: the drying in the step 3) is drying for 1-3 hours at the temperature of 100-110 ℃.
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| CN201710265227.2A CN107235732B (en) | 2017-04-21 | 2017-04-21 | Mullite coated refractory material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57110631A (en) * | 1980-12-26 | 1982-07-09 | Kawasaki Refract Co Ltd | Coating material of immersion lance for refinging molten metal |
| CN101439979A (en) * | 2008-12-13 | 2009-05-27 | 郑州顺兴耐火材料有限公司 | High refractoriness under load and thermal shock resistant fireproof brick |
| CN101475390A (en) * | 2009-01-16 | 2009-07-08 | 张命荣 | Al2O3/ZrO2 refractory casting material and using method thereof |
| CN105753487A (en) * | 2016-03-01 | 2016-07-13 | 中钢集团洛阳耐火材料研究院有限公司 | Composite powder for improving scouring resistance of carbon-containing refractory material and preparation method of composite powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57110631A (en) * | 1980-12-26 | 1982-07-09 | Kawasaki Refract Co Ltd | Coating material of immersion lance for refinging molten metal |
| CN101439979A (en) * | 2008-12-13 | 2009-05-27 | 郑州顺兴耐火材料有限公司 | High refractoriness under load and thermal shock resistant fireproof brick |
| CN101475390A (en) * | 2009-01-16 | 2009-07-08 | 张命荣 | Al2O3/ZrO2 refractory casting material and using method thereof |
| CN105753487A (en) * | 2016-03-01 | 2016-07-13 | 中钢集团洛阳耐火材料研究院有限公司 | Composite powder for improving scouring resistance of carbon-containing refractory material and preparation method of composite powder |
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