CN115108843B - Long-life spalling-resistant 90t arc furnace roof mullite prefabricated part and preparation method thereof - Google Patents
Long-life spalling-resistant 90t arc furnace roof mullite prefabricated part and preparation method thereof Download PDFInfo
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- CN115108843B CN115108843B CN202210733903.5A CN202210733903A CN115108843B CN 115108843 B CN115108843 B CN 115108843B CN 202210733903 A CN202210733903 A CN 202210733903A CN 115108843 B CN115108843 B CN 115108843B
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- resistant
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 71
- 238000004901 spalling Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 239000004568 cement Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000010431 corundum Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010891 electric arc Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- 238000000227 grinding Methods 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009751 slip forming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/74—Ceramic products containing macroscopic reinforcing agents containing shaped metallic materials
- C04B35/76—Fibres, filaments, whiskers, platelets, or the like
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- 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
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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Abstract
The application relates to a long-life spalling-resistant 90t arc furnace roof mullite prefabricated part and a preparation method thereof, wherein the raw materials of the prefabricated part comprise mullite particles, 5-10wt% of corundum particles, 1-3wt% of steel fibers and 5-17wt% of alpha-Al 2 O 3 Fine powder, 10 to 30 weight percent of mullite fine powder, 0.2 to 2 weight percent of silicon micro powder and 1 to 2 weight percent of rho-Al 2 O 3 The micro powder and 3 to 7 weight percent of calcium aluminate cement fine powder are added with 0.1 to 1 weight percent of water reducer and 5 to 7 weight percent of water. The application improves the service life of the prefabricated member from 205 to 253 times to 309 to 355 times, and changes the original peeling damage into the expiration of the electric furnace service to replace the prefabricated member.
Description
Technical Field
The application relates to the field of refractory materials, in particular to a long-life spalling-resistant 90t arc furnace roof mullite prefabricated member and a preparation method thereof.
Background
In the using process of the arc furnace top prefabricated member, the prefabricated member needs to bear extremely high electrode temperature and is in a high-temperature state for a long time; often affected by sudden changes in temperature; can also be eroded by the chemical attack of furnace gas and slag powder, the radiation of arc laser and the scouring of smoke dust; the dust accumulation of the prefabricated member can generate pressure and prevent heat dissipation; in addition to vibration during the rotation of the furnace roof in the lifting direction, these large parts promote the propagation of cracks in the preforms, leading to flaking.
The mullite refractory material has the advantages of good thermal shock stability, high refractoriness, small thermal expansion coefficient, small change of a re-firing line, good wear resistance and the like, and is widely applied to an electric furnace top prefabricated member. Although the addition of steel fibers can improve the fracture toughness of the refractory material, cracks are larger during thermal spalling, and the steel fibers are easy to melt and fracture due to the high temperature of the graphite electrode, so that the problem of large-scale spalling of the prefabricated part cannot be basically solved.
At present, the preparation of furnace top prefabricated parts of an electric arc furnace is studied: the furnace cover of the electric furnace and the material (CN 201911278117.5) thereof are applicable to the electric furnace with the length of 40t, and cannot be applicable to the electric furnace with the length of 90t, and the service life of the furnace cover is 150 times at maximum, so that the production requirement of the electric arc furnace with the length of 90t is difficult to meet; for another example, the service life of the furnace cover center piece of the electric furnace and the material (CN 201911278119.4) thereof is 60-80 times, the service life of the electric furnace is 15t, the electric furnace is low in service life and not environment-friendly, and the electric furnace gradually exits from the market.
Disclosure of Invention
Aiming at the situation, the application aims to overcome the defects of the prior art, and aims to provide the long-life spalling-resistant 90t arc furnace roof mullite prefabricated member and the preparation method thereof, and the prepared long-life spalling-resistant 90t arc furnace roof mullite prefabricated member has longer service life, good high-temperature volume stability, strong spalling resistance, capability of avoiding molten steel splashing caused by thermal spalling and high safety.
The technical scheme of the application is as follows:
a preparation method of long-life spalling-resistant 90t arc furnace roof mullite prefabricated part,
the method comprises the following steps:
step one: 5 to 17 weight percent of alpha-Al 2 O 3 Fine powder, 10 to 30 weight percent of mullite fine powder, 0.2 to 2 percent of silicon fine powder and 1 to the upper part2wt% of ρ -Al 2 O 3 Mixing the micro powder and 3-7wt% of calcium aluminate cement fine powder in a mixer for 4-6 hours to obtain matrix fine powder after mixing;
step two: placing 50-65wt% of mullite particles and 5-10wt% of corundum particles into a stirrer to stir for 0.1-0.3 h, and adding 1-3wt% of steel fibers while stirring; adding the matrix fine powder, uniformly stirring, adding 2-3wt% of uniformly mixed water and water reducer mixed liquid, and finally adding 3-4wt% of water to obtain castable;
step three: placing a grinding tool on a vibration table, pouring the castable into the grinding tool, opening the vibration table to vibrate when the castable is filled to 1/3 of the position, then adding the rest castable, keeping the surface of the castable for 1-3 min after the surface vibration is leveled, curing for 24-48h at normal temperature, demolding, baking for 72-108 h at 260-300 ℃, and cooling to obtain the long-life spalling-resistant 90t arc furnace roof mullite prefabricated member.
Further, the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part comprises the steps of 2 O 3 The granularity of the fine powder is less than or equal to 0.088mm, al 2 O 3 The content is more than 95wt%; the granularity of the corundum particles is 1-5 mm, al 2 O 3 The content is more than 99wt%; said ρ -Al 2 O 3 The granularity of the micro powder is less than or equal to 0.013mm.
Further, according to the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part, the granularity of the mullite fine powder is less than or equal to 0.088mm, and Al is contained in the mullite fine powder 2 O 3 The content is more than 60wt%; the grain size of the mullite is 3-8 mm, al 2 O 3 The content is more than 60wt percent, K 2 O+Na 2 The O content is not more than 0.5wt%.
Furthermore, the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part comprises the steps that the granularity of the silica micropowder is less than or equal to 0.026mm, the median diameter is 0.0070 mm, and the SiO is prepared by the steps of 2 The content is more than 97wt%.
Further, the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated partThe granularity of the calcium aluminate cement fine powder is less than or equal to 0.074mm, and Al 2 O 3 The content is more than 69wt%.
Furthermore, according to the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part, the steel fiber is 300-series austenitic stainless steel.
Furthermore, according to the preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part, the thickness of the mold is more than 10mm, and the positioning hole is fixed and has no deformation.
Furthermore, the frequency range of the vibration table is 0.4-50 Hz, and the bearing weight is more than 10t.
Further, in the preparation method of the long-life spalling-resistant 90t electric arc furnace roof mullite prefabricated part, the water reducing agent is two or more of lignosulfonate, polycyclic aromatic sulfonate and water-soluble resin.
Further, a long-life spalling-resistant 90t arc furnace roof mullite preform is produced by the method of any one of the above.
Compared with the prior art, the application has the following beneficial effects:
the composite water reducer is adopted, so that the agglomeration of water and fine powder can be destroyed to a great extent, the water consumption is effectively reduced, and the high-temperature performance of the prefabricated member is ensured; the pouring materials are added into the water by mixing the composite water reducer, so that the water reducing effect of the water reducer can be exerted to the greatest extent, and then water is added for the second time, and the water consumption is obviously reduced due to the fact that the aggregates among the fine powder are destroyed, the uniformity of water distribution can be improved, the pouring performance is greatly improved during pouring, and the pouring time is obviously shortened; the reduction of water consumption can also reduce the maintenance and baking time of the material, prevent hydration of the material and prevent peeling phenomenon caused by overlarge internal stress due to hydration in the high-temperature use process.
The addition of the calcium aluminate cement can effectively ensure the performance of the material at normal temperature and during baking, and prevent deformation; the cementing system formed by cement can also reduce the generation of cracks of the material in the curing and baking processes, and improves the stripping resistance of the material.
Cement will fail at high temperatures, so two other binders ρ -Al are added 2 O 3 And silicon micropowder, on the one hand, in the high-temperature use process, rho-Al 2 O 3 The mullite formed by the mullite and the silica powder can effectively prevent crack growth, and can repair microcracks formed in a matrix in the use process, so that the peeling is avoided; on the other hand, ρ -Al 2 O 3 The ceramic joint is formed by reacting with mullite particles, and the ceramic joint is formed by reacting with silicon micropowder and corundum particles, so that aggregate and matrix are connected together due to the existence of the ceramic joint, the high-temperature strength of the prefabricated member is effectively improved, a crack propagation source is prevented from being formed between the aggregate and the matrix, and the formation of cracks is avoided; as the mullite can be continuously formed, the volume shrinkage caused by high-temperature sintering is effectively avoided, and the high-temperature volume stability of the prefabricated member is ensured; because the crack cannot be continuously expanded under the formation of mullite, the steel fiber is protected from being exposed to the high-temperature electrode at high temperature due to the protection of the castable, the steel fiber is preserved, the fiber toughening of the steel fiber can be effectively exerted, and the service life and the safety of the prefabricated part are further improved.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part prepared by the application is detected by the following steps: the apparent porosity is 8.2-20.9%; the volume density is 2.44-2.73/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength is 72-136 MPa; the wear resistance is 3.0-3.5 cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The change of the re-burning line is-0.03 to 0.04 percent; softening temperature under load T 0.6 The creep rate (1550 ℃ and 50 h) is more than 1600 ℃ and less than 0.19%, and the main phase composition is mullite and corundum.
Therefore, the application can stop the occurrence of thermal spalling in one furnace service, has longer service life, good high-temperature volume stability and strong spalling resistance, can stop the splashing of molten steel caused by thermal spalling, and has high safety.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The reagents or instruments used in the examples of the present application were not manufacturer-identified and were conventional reagent products commercially available.
In order to avoid repetition, the equipment and materials related to the specific embodiments are described in the following in a unified manner, and the embodiments are not repeated:
the alpha-Al 2 O 3 The granularity of the fine powder is less than or equal to 0.088mm, al 2 O 3 The content is more than 95wt%; the granularity of the corundum particles is 1-5 mm, al 2 O 3 The content is more than 99wt%; said ρ -Al 2 O 3 The granularity of the micro powder is less than or equal to 0.013mm.
The granularity of the mullite fine powder is less than or equal to 0.088mm, al 2 O 3 The content is more than 60wt%; the grain size of the mullite is 3-8 mm, al 2 O 3 The content is more than 60wt percent, K 2 O+Na 2 The O content is not more than 0.5wt%.
The granularity of the silicon micropowder is less than or equal to 0.026mm, the median diameter is 0.0070 mm, and the SiO is 2 The content is more than 97wt%.
The granularity of the calcium aluminate cement fine powder is less than or equal to 0.074mm, and Al 2 O 3 The content is more than 69wt%.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part and the preparation method thereof are characterized in that the steel fiber is 300-series austenitic stainless steel.
The thickness of the die is larger than 10mm, and the positioning hole is fixed and has no deformation.
The frequency range of the vibration table is 0.4-50 Hz, and the bearing weight is more than 10t.
The water reducer is two or more of lignosulfonate, polycyclic aromatic sulfonate and water-soluble resin.
Example 1
A preparation method of long-life spalling-resistant 90t arc furnace roof mullite prefabricated part.
The preparation method of the embodiment comprises the following steps:
step one: 7 to 17 weight percent of alpha-Al 2 O 3 Fine powder, 20 to 30 weight percent of mullite fine powder, 0.2 to 2 weight percent of silicon micro powder and 1 to 2 weight percent of rho-Al 2 O 3 Mixing the micropowder and 3-5 wt% of calcium aluminate cement fine powder in a mixer for 4-5 h to obtain matrix fine powder after the mixing.
Step two: placing 50-55wt% of mullite particles and 5-8wt% of corundum particles into a stirrer to stir for 0.1-0.2 h, and adding 1-3wt% of steel fibers while stirring; and adding the matrix fine powder, uniformly stirring, adding 2-3wt% of uniformly mixed water and water reducer mixed liquid, and finally adding 3-4wt% of water to obtain the castable.
Step three: placing a grinding tool on a vibration table, pouring the castable into the grinding tool, opening the vibration table to vibrate when the castable is filled to 1/3 of the position, then adding the rest castable, keeping for 1-3 min after the surface vibration is leveled, demoulding after curing for 24-48h at normal temperature, baking for 72-108 h at 260-300 ℃, and cooling to obtain the long-life spalling-resistant 90t arc furnace roof mullite prefabricated member.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part prepared by the embodiment is detected: after one electric furnace service process, the service life is 318 times, and the residual thickness of the prefabricated part is 345mm (the thickness is 610mm before use).
Example 2
A preparation method of long-life spalling-resistant 90t arc furnace roof mullite prefabricated part.
The preparation method of the embodiment comprises the following steps:
step one: 6 to 14 weight percent of alpha-Al 2 O 3 Fine powder, 15 to 20 weight percent of mullite fine powder, 0.2 to 2 weight percent of silicon micro powder and 1 to 2 weight percent of rho-Al 2 O 3 Mixing the micropowder and 4-6wt% of calcium aluminate cement fine powder in a mixer for 4-5 h to obtain matrix fine powder after mixing.
Step two: placing 55-60 wt% of mullite particles and 6-9 wt% of corundum particles into a stirrer to stir for 0.1-0.2 h, and adding 1-3 wt% of steel fibers while stirring; and adding the matrix fine powder, uniformly stirring, adding 2-3wt% of uniformly mixed water and water reducer mixed liquid, and finally adding 3-4wt% of water to obtain the castable.
Step three: placing a grinding tool on a vibration table, pouring the castable into the grinding tool, opening the vibration table to vibrate when the castable is filled to 1/3 of the position, then adding the rest castable, keeping the surface of the castable for 1-3 min after the surface vibration is leveled, curing for 24-48h at normal temperature, demolding, baking for 72-108 h at 260-300 ℃, and cooling to obtain the long-life spalling-resistant 90t arc furnace roof mullite prefabricated member.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part prepared by the embodiment is detected: after three electric furnace processes, the service life is 337-355 times, and the residual thickness of the prefabricated member is 487-523 mm (the thickness is 610mm before use).
Example 3
A preparation method of long-life spalling-resistant 90t arc furnace roof mullite prefabricated part.
The preparation method of the embodiment comprises the following steps:
step one: 5 to 11 weight percent of alpha-Al 2 O 3 Fine powder, 10 to 20 weight percent of mullite fine powder, 0.2 to 2 weight percent of silicon micro powder and 1 to 2 weight percent of rho-Al 2 O 3 Mixing the micropowder and 5-7wt% of calcium aluminate cement fine powder in a mixer for 5-6 h to obtain matrix fine powder after mixing.
Step two: placing 60-65wt% of mullite particles and 7-10wt% of corundum particles into a stirrer to stir for 0.2-0.3 h, and adding 1-3wt% of steel fibers while stirring; and adding the matrix fine powder, uniformly stirring, adding 2-3wt% of uniformly mixed water and water reducer mixed liquid, and finally adding 3-4wt% of water to obtain the castable.
Step three: placing a grinding tool on a vibration table, pouring the castable into the grinding tool, opening the vibration table to vibrate when the castable is filled to 1/3 of the position, then adding the rest castable, keeping the surface of the castable for 1-3 min after the surface vibration is leveled, curing for 24-48h at normal temperature, demolding, baking for 72-108 h at 260-300 ℃, and cooling to obtain the long-life spalling-resistant 90t arc furnace roof mullite prefabricated member.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part prepared by the embodiment is detected: after one electric furnace service process, the service life is 329 times, and the residual thickness of the prefabricated part after use is 386mm (the thickness is 610mm before use).
The embodiment of the application adopts the specific value correlation detection results as follows:
comparison of detection data related to the examples and comparative examples of the present application:
wherein, mullite grains in the comparative example are replaced by 88-grade high aluminum grains of 0-10 mm. The curing times of examples 1-3 and comparative examples were 24-48 hours, and the baking was at 260-300℃for 72-108 hours.
Compared with the prior art, the embodiment has the following positive effects:
in the specific embodiment, due to the adoption of the composite water reducing agent, the agglomeration of water and fine powder can be destroyed to a great extent, the water consumption is effectively reduced, and the high-temperature performance of the prefabricated member is ensured; the pouring materials are added into the water by mixing the composite water reducer, so that the water reducing effect of the water reducer can be exerted to the greatest extent, and then water is added for the second time, and the water consumption is obviously reduced due to the fact that the aggregates among the fine powder are destroyed, the uniformity of water distribution can be improved, the pouring performance is greatly improved during pouring, and the pouring time is obviously shortened; the reduction of water consumption can also reduce the maintenance and baking time of the material, prevent hydration of the material and prevent peeling phenomenon caused by overlarge internal stress due to hydration in the high-temperature use process.
The addition of the calcium aluminate cement can effectively ensure the performance of the material at normal temperature and during baking, and prevent deformation; the cementing system formed by cement can also reduce the generation of cracks of the material in the curing and baking processes, and improves the stripping resistance of the material.
Cement will fail at high temperatures, so two other binders ρ -Al are added 2 O 3 And silicon micropowder, on the one hand, in the high-temperature use process, rho-Al 2 O 3 The mullite formed by the mullite and the silica powder can effectively prevent crack growth, and can repair microcracks formed in a matrix in the use process, so that the peeling is avoided; on the other hand, ρ -Al 2 O 3 The ceramic joint is formed by reacting with mullite particles, and the ceramic joint is formed by reacting with silicon micropowder and corundum particles, so that aggregate and matrix are connected together due to the existence of the ceramic joint, the high-temperature strength of the prefabricated member is effectively improved, a crack propagation source is prevented from being formed between the aggregate and the matrix, and the formation of cracks is avoided; as the mullite can be continuously formed, the volume shrinkage caused by high-temperature sintering is effectively avoided, and the high-temperature volume stability of the prefabricated member is ensured; because the crack cannot be continuously expanded under the formation of mullite, the steel fiber is protected from being exposed to the high-temperature electrode at high temperature due to the protection of the castable, the steel fiber is preserved, the fiber toughening of the steel fiber can be effectively exerted, and the service life and the safety of the prefabricated part are further improved.
The long-life spalling-resistant 90t arc furnace roof mullite prefabricated part prepared by the specific embodiment is detected: the apparent porosity is 8.2-20.9%; the volume density is 2.44-2.73/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compressive strength is 72-136 MPa; the wear resistance is 1.0-3.5 cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The change of the re-burning line is-0.03 to 0.04 percent; softening temperature under load T 0.6 A creep rate (1550 ℃ for 50 h) of more than 1600 ℃ and less than 0.19%, and a main characteristicThe composition of the essential phases is mullite and corundum.
Therefore, the application can stop the occurrence of thermal spalling in one furnace service, has longer service life, good high-temperature volume stability and strong spalling resistance, can stop the splashing of molten steel caused by thermal spalling, and has high safety.
The above examples represent only a limited number of preferred embodiments of the application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application.
Claims (9)
1. The preparation method of the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part is characterized by comprising the following steps of:
step one: mixing 5-17 wt% of alpha-Al 2O3 fine powder, 10-30 wt% of mullite fine powder, 0.2-2 of silicon fine powder, 1-2 wt% of rho-Al 2O3 fine powder and 3-7 wt% of calcium aluminate cement fine powder in a mixer for 4-6 h to obtain matrix fine powder after mixing;
step two: placing 50-65wt% of mullite particles and 5-10wt% of corundum particles into a stirrer to stir for 0.1-0.3 h, and adding 1-3wt% of steel fibers while stirring; adding the matrix fine powder, uniformly stirring, adding 2-3wt% of uniformly mixed water and water reducer mixed liquid, and finally adding 3-4wt% of water to obtain castable;
step three: placing a mould on a vibration table, pouring the castable into the mould, opening the vibration table to vibrate when the mould is filled to 1/3 of the position, then adding the rest castable, keeping the surface of the castable for 1-3 min after the surface vibration is smooth, curing for 24-30 h at normal temperature, demoulding, baking for 72-84 h at 260-300 ℃, and cooling to obtain the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part;
the water reducer is two or more of lignosulfonate, polycyclic aromatic sulfonate and water-soluble resin.
2. The method for preparing the long-life spalling-resistant 90t electric arc furnace roof mullite prefabricated part, according to claim 1, is characterized in that the granularity of the alpha-Al 2O3 fine powder is less than or equal to 0.088mm, and the content of Al2O3 is more than 95wt%; the granularity of the corundum particles is 1-5 mm, and the content of Al2O3 is more than 99wt%; the granularity of the rho-Al 2O3 micro powder is less than or equal to 0.013mm.
3. The method for preparing the long-life spalling-resistant 90t arc furnace roof mullite preform as claimed in claim 1, wherein the granularity of the mullite fine powder is less than or equal to 0.088mm, and the Al2O3 content is more than 60wt%; the grain size of the mullite is 3-8 mm, the content of Al2O3 is more than 60wt%, and the content of K2O+Na2O is not more than 0.5wt%.
4. The method for preparing the long-life spalling-resistant 90t arc furnace roof mullite preform of claim 1, wherein the granularity of the silica micropowder is less than or equal to 0.026mm, the median diameter is 0.007mm, and the content of SiO2 is more than 97wt%.
5. The method for preparing the long-life spalling-resistant 90t electric arc furnace roof mullite preform of claim 1, wherein the granularity of the calcium aluminate cement fine powder is less than or equal to 0.074mm, and the Al2O3 content is more than 69wt%.
6. The method for producing long life spalling resistant 90t arc furnace roof mullite pre-form of claim 1 wherein the steel fiber is 300 series austenitic stainless steel.
7. The method for preparing the long-life spalling-resistant 90t arc furnace roof mullite preform of claim 1, wherein the thickness of the mold is more than 10mm, and the positioning hole is fixed and has no deformation.
8. The method for preparing the long-life spalling-resistant 90t arc furnace roof mullite prefabricated part, according to claim 1, is characterized in that the frequency range of the vibrating table is 0.4-50 Hz, and the bearing weight is more than 10t.
9. A long life spalling resistant 90t arc furnace roof mullite preform produced by the method of any one of claims 1-8.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960738A (en) * | 1987-11-02 | 1990-10-02 | Kureha Chemical Industry Co., Ltd. | Mullite-alumina composite sintered body and process for producing the same |
| KR19990033470A (en) * | 1997-10-24 | 1999-05-15 | 한종웅 | Refractory material embedded in an industrial furnace and manufacturing method thereof |
| WO2004043852A1 (en) * | 2002-11-11 | 2004-05-27 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
| CN1513813A (en) * | 2002-12-31 | 2004-07-21 | 上海美迪彩瓦有限公司 | Light heatinsulating concrete coloured roof artistic tile and its making method |
| JP2012072051A (en) * | 2010-08-31 | 2012-04-12 | Agc Ceramics Co Ltd | Powder composition for fireproof castable, and fireproof castable using the same |
| CN104355634A (en) * | 2014-10-28 | 2015-02-18 | 北京利尔高温材料股份有限公司 | Alumina electric furnace cover and preparation method thereof |
| CN104402469A (en) * | 2014-11-13 | 2015-03-11 | 北京利尔高温材料股份有限公司 | Electric furnace top central area furnace cover and preparation method thereof |
| CN107311680A (en) * | 2017-07-28 | 2017-11-03 | 武汉科技大学 | A kind of lightweight corundum-mullite castable and preparation method thereof |
| AU2016272432A1 (en) * | 2015-06-05 | 2017-12-07 | Johnson Matthey Public Limited Company | Method for preparing a sorbent |
| CN107473658A (en) * | 2017-08-18 | 2017-12-15 | 东南大学 | A kind of material of ultra-high performance concrete containing coarse aggregate and preparation method thereof |
| CN107759212A (en) * | 2017-11-01 | 2018-03-06 | 安徽马钢耐火材料有限公司 | A kind of middle clad mullite castable and its production method |
| CN111732422A (en) * | 2020-05-29 | 2020-10-02 | 郑州安耐克实业有限公司 | Electric furnace roof prefabricated part with strong thermal shock resistance and preparation process thereof |
| CN113264738A (en) * | 2021-06-24 | 2021-08-17 | 郑州大学 | High-performance cement-based composite material and preparation method thereof |
| CN114044653A (en) * | 2021-11-15 | 2022-02-15 | 山东昊翔工程材料科技有限公司 | Novel high-ductility concrete and preparation method and equipment thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11078119B2 (en) * | 2014-10-23 | 2021-08-03 | Ashapura Minechem Ltd. | Composites of sintered mullite reinforced corundum granules and method for its preparation |
-
2022
- 2022-06-27 CN CN202210733903.5A patent/CN115108843B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960738A (en) * | 1987-11-02 | 1990-10-02 | Kureha Chemical Industry Co., Ltd. | Mullite-alumina composite sintered body and process for producing the same |
| KR19990033470A (en) * | 1997-10-24 | 1999-05-15 | 한종웅 | Refractory material embedded in an industrial furnace and manufacturing method thereof |
| WO2004043852A1 (en) * | 2002-11-11 | 2004-05-27 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
| CN1513813A (en) * | 2002-12-31 | 2004-07-21 | 上海美迪彩瓦有限公司 | Light heatinsulating concrete coloured roof artistic tile and its making method |
| JP2012072051A (en) * | 2010-08-31 | 2012-04-12 | Agc Ceramics Co Ltd | Powder composition for fireproof castable, and fireproof castable using the same |
| CN104355634A (en) * | 2014-10-28 | 2015-02-18 | 北京利尔高温材料股份有限公司 | Alumina electric furnace cover and preparation method thereof |
| CN104402469A (en) * | 2014-11-13 | 2015-03-11 | 北京利尔高温材料股份有限公司 | Electric furnace top central area furnace cover and preparation method thereof |
| AU2016272432A1 (en) * | 2015-06-05 | 2017-12-07 | Johnson Matthey Public Limited Company | Method for preparing a sorbent |
| CN107311680A (en) * | 2017-07-28 | 2017-11-03 | 武汉科技大学 | A kind of lightweight corundum-mullite castable and preparation method thereof |
| CN107473658A (en) * | 2017-08-18 | 2017-12-15 | 东南大学 | A kind of material of ultra-high performance concrete containing coarse aggregate and preparation method thereof |
| CN107759212A (en) * | 2017-11-01 | 2018-03-06 | 安徽马钢耐火材料有限公司 | A kind of middle clad mullite castable and its production method |
| CN111732422A (en) * | 2020-05-29 | 2020-10-02 | 郑州安耐克实业有限公司 | Electric furnace roof prefabricated part with strong thermal shock resistance and preparation process thereof |
| CN113264738A (en) * | 2021-06-24 | 2021-08-17 | 郑州大学 | High-performance cement-based composite material and preparation method thereof |
| CN114044653A (en) * | 2021-11-15 | 2022-02-15 | 山东昊翔工程材料科技有限公司 | Novel high-ductility concrete and preparation method and equipment thereof |
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