CN116287534A - Low-carbon composite converter tapping hole brick and preparation method thereof - Google Patents
Low-carbon composite converter tapping hole brick and preparation method thereof Download PDFInfo
- Publication number
- CN116287534A CN116287534A CN202310104107.XA CN202310104107A CN116287534A CN 116287534 A CN116287534 A CN 116287534A CN 202310104107 A CN202310104107 A CN 202310104107A CN 116287534 A CN116287534 A CN 116287534A
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- Prior art keywords
- carbon
- low
- carbon part
- hole brick
- inner layer
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 105
- 239000011449 brick Substances 0.000 title claims abstract description 98
- 238000010079 rubber tapping Methods 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 48
- 239000010959 steel Substances 0.000 claims abstract description 48
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- 238000000034 method Methods 0.000 claims abstract description 11
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- 238000011049 filling Methods 0.000 claims abstract 2
- 238000000197 pyrolysis Methods 0.000 claims abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 128
- 239000000395 magnesium oxide Substances 0.000 claims description 64
- 239000000843 powder Substances 0.000 claims description 43
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
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- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 10
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 1
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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
- C04B35/01—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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
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- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
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Abstract
The invention discloses a low-carbon composite converter tapping hole brick and a preparation method thereof, and belongs to the field of refractory materials. The steel tapping hole is made of composite materials and comprises an outer layer high-carbon part and an inner layer low-carbon part from outside to inside in the radial direction, wherein the carbon content of the outer layer high-carbon part is 10% -20%, and the carbon content of the inner layer low-carbon part is 3% -6%; the preparation method comprises the following steps: respectively preparing raw materials of an outer high-carbon part and an inner low-carbon part after high-speed mixing, forming the outer high-carbon part and the inner low-carbon part by high-pressure molding after die filling, and then sequentially drying, soaking oil, dry distillation and sand removal to obtain a finished product. According to the invention, through formula optimization and combination and process compounding improvement, the graphite usage amount is reduced, the tap hole is further enabled to be low in carbonization and tissue densification, the problem of oxidation of graphite in bricks by high-oxidability slag is avoided, and the service life of the steel outlet is greatly prolonged.
Description
Technical Field
The invention belongs to the field of refractory materials, and particularly relates to a low-carbon composite converter tapping hole brick and a preparation method thereof.
Background
In the converter steelmaking process, the converter is protected by charging, converting, deoxidizing and tapping, and slag splashing, the tapping hole is subjected to sharp temperature change and oxygen change, and high thermal shock resistance and oxidation resistance are required. In the tapping process, the steel is simultaneously eroded by molten steel, and the steel has wear resistance and slag resistance. The service life of the converter tapping hole is an important index for measuring the continuous operation rate of the converter, directly influences the converter efficiency and the quality of molten steel, and plays an important role in the steelmaking process. Therefore, the service life of the converter tapping hole brick is prolonged, and the method has important significance for improving the production efficiency of the converter and reducing the production cost. When steel enterprises make steel in a converter, the service life of a steel tapping hole brick is expected to be prolonged to improve the operation rate of the converter, so that the productivity of the converter is increased. The magnesia carbon brick is widely used in all parts of the lining of a converter with excellent slag resistance and thermal shock stability, and the magnesia carbon steel tapping hole has better effect, but because of the special requirements of the smelting process, the carbon contained in the working face of the brick is firstly blown into O when being blown into oxygen for smelting in the using process of the magnesia carbon steel tapping hole 2 And oxidation of FeO and the like in the oxidizing slag and reduction of MgO at high temperature, so that a decarburized layer is formed on the steel outlet surface. Due to the oxidization removal of carbon, the brick body tissue is loosened and embrittled, and is worn under the flushing of molten steel during tapping. Meanwhile, due to the removal of carbon and the loosening of brick bodies, slag permeates into a decarburized layer and reacts with magnesia particles to cause melting loss. The main cause of the magnesium carbon tap hole damage is oxidation of carbon, followed by spalling due to wear and rapid temperature changes. In order to improve the quality of the magnesium-carbon steel tapping hole and prolong the service life of the magnesium-carbon steel tapping hole, the magnesium-carbon steel tapping hole must be improvedCompactness, prevents oxidation of carbon and improves its high temperature strength. And the steel mill generally adopts magnesia carbon tapping hole bricks at present. Because the graphite content in the magnesia carbon steel tapping hole brick is about 20%, the compactness of the magnesia carbon steel tapping hole brick must be improved and the high-temperature strength of the magnesia carbon steel tapping hole brick must be improved in order to improve the quality of the magnesia carbon steel tapping hole and prolong the service life of the magnesia carbon steel tapping hole, so the development of the steel tapping brick with strong scouring resistance, erosion resistance and oxidation resistance for high-temperature molten steel and slag is of great significance for converter steelmaking.
For example, the Chinese patent application No. 202010228101.X, the application publication date is 2020, 06 and 19, discloses a low-carbon magnesia carbon brick for ladle slag line and a preparation method thereof. The low-carbon magnesia carbon brick adopts high-activity metal composite powder (Al powder, si powder, silicon carbide and boron carbide) to be added into magnesia carbon alkaline materials, the carbon content is reduced from 10 to 18 percent to below 5 percent, good thermal shock stability and high-temperature strength are maintained, oxidation resistance and slag resistance are improved, and the low-carbon magnesia carbon brick is suitable for the requirements of clean smelting. However, after the carbon content is reduced, the service life of the ladle is greatly influenced, and the ladle is used in an on-line mode and an off-line mode. There are large temperature differences and temperature drops in online turnover. The thermal conductivity of the magnesia carbon brick is reduced after the carbon content is reduced, so that the capability of the material for relieving thermal stress generated when the temperature suddenly changes is reduced, and the thermal shock resistance of the low-carbon magnesia carbon brick is reduced to generate large-area spalling and cracking; secondly, after the carbon content is reduced, the wettability of slag and materials is enhanced, and graphite is used as a single carbon source to reduce the slag erosion resistance permeability of the magnesia carbon brick.
The Chinese patent application number is 201710586908.9, and the application publication date is 2017, 10 month and 24 days, and discloses a low-carbon magnesia carbon brick for a ladle and a preparation method thereof. The magnesia-zirconia-sand is used for replacing part of fused magnesia to manufacture the low-carbon magnesia-carbon brick, the fused magnesia, the magnesia-zirconia-sand and the crystalline flake graphite with different grain compositions are used as main raw materials, phenolic resin and modified asphalt are used as binding agents, and antioxidants are added to improve the thermal shock resistance stability and the permeation resistance of the low-carbon magnesia-carbon brick. However, when a large amount of magnesium zirconium sand is added, zirconia crystal phases are mutually converted in high-temperature use, so that volume expansion and shrinkage are caused, a large amount of microcracks are generated in the product in use, the number of microcracks is increased, crack strings are easily formed, the body is cracked, the strength is reduced, meanwhile, the oxygen diffusion channels are increased, and the overall oxidation resistance is reduced, so that the overall service life and stability of the steel ladle are not facilitated.
Disclosure of Invention
1. Problems to be solved
The invention provides a low-carbon composite converter tapping hole brick, and aims to optimize the material of the converter tapping hole brick so as to improve the usability of the converter tapping hole brick.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the tapping hole brick for the low-carbon composite converter comprises an outer high-carbon part and an inner low-carbon part from outside to inside in the radial direction, wherein the carbon content of the outer high-carbon part is 10% -20% and the carbon content of the inner low-carbon part is 3% -6% as measured by a high-frequency furnace combustion infrared absorption method. The high carbon part of the outer layer has high graphite content, greatly improves the thermal stress absorption, and can also have stronger thermal shock resistance so as to comprehensively improve the service life of the steel tapping hole.
The high-carbon part on the outer layer avoids the problems of the low-carbon magnesia carbon brick, and the low-carbon part on the inner layer is filled in the pores of the material by introducing various composite high-efficiency carbons, so that the carbonized material has uniform and compact structure and better performance. Meanwhile, the service conditions of the steel tapping hole are greatly different from those of a steel ladle, the steel tapping hole is positioned in the converter, the temperature is always kept above 1000 ℃, and no large temperature drop and rapid cooling and heating exist.
Further, the thickness of the outer layer high carbon part in the radial direction of the steel tapping hole brick accounts for 60-90%; the thickness of the inner layer low carbon part accounts for 10-40%.
Further, the raw material composition of the outer high carbon part and the raw material composition of the inner low carbon part both contain MgO and B 4 C。
Further, the outer layer high carbon part is composed of an outer layer composite material and a forming binder, wherein the outer layer composite material comprises the following raw materials in parts by weight:
40-60 parts of 99 large-crystal fused magnesia particles;
8-18 parts of 99 large-crystal fused magnesia fine powder;
10-20 parts of flake graphite;
1-6 parts of aluminum-tungsten alloy;
2-4 parts of metal silicon powder;
1-2 parts of high-temperature asphalt powder;
0.5 to 2 portions of boron carbide.
Further, the inner layer low-carbon part is composed of an inner layer composite material and a forming binder, wherein the inner layer composite material comprises the following raw materials in parts by weight:
50-70 parts of 99 large-crystal fused magnesia particles;
8-18 parts of 99 large-crystal fused magnesia fine powder;
2-10 parts of nano alumina powder;
2-4 parts of carbon black;
4-8 parts of aluminum-tungsten alloy;
1-4 parts of boron nitride powder;
0.5 to 2 parts of boron carbide;
0.5 to 1 part of calcium boride.
The low carbon material with excellent corrosion resistance is arranged at the low carbon part of the inner layer, the carbon consumption of graphite and the like is reduced, the oxidation speed is reduced, the structure is densified, borate is formed on the contact surface of the flowing steel, and the carbon between magnesite is sealed in a bridge form, so that the further oxidation is avoided; wherein the reaction principle is as follows:
B 4 C(s)+3O 2 (g)→2B 2 O 3 (1)+C(s)
B 4 C(s)+6CO(g)→2B 2 O 3 (1)+7C(s)
3MgO(s)+B 2 O 3 (1)→3MgO·B 2 O 3 magnesium borate
B 4 C(s)+7CO 2 (g)→2B 2 O 3 (1)+8CO(g)
4Al( l) + 3C( s) →Al 4 C 3 (s)
Al 4 C 3 (s)+6CO(g)→2Al 2 O 3 (s)+9C(s)
2Al(l)+3CO(g)→Al 2 O 3 (s)+3C(s)
2Al(l)+3MgO(s)→Al 2 O 3 (s)+3Mg(g)
Al 2 O 3 (s)+MgO(s)→MgAl 2 O 4 (s)
B 2 O 3 +Al 2 O 3 →2Al 2 O 3 ·B 2 O 3
The magnesium borate produced has good wettability to MgO and poor wettability to graphite. The carbon is protected, not by wrapping carbon, but by connecting MgO with borate to form a bridge-like structure, magnesia particles and borate bridge form a compact protection layer, the surface of the brick is sealed, and the invasion of oxygen is blocked.
The aluminum oxide or the compound which generates the aluminum oxide at high temperature reacts with the boron oxide, and the boron oxide simultaneously plays a role of a fluxing agent, so that the aluminum borate whisker is finally obtained.
The high-efficiency composite antioxidant nanoscale carbon black and boron carbide are introduced, so that the spalling resistance, erosion resistance and oxidation resistance of the low-carbon magnesia carbon brick are improved.
Further, the molding binder comprises a liquid phenolic resin, wherein the phenolic resin w (C solid content) is more than or equal to 50 percent, and the molding binder comprises the following components in percentage by weight:
in the outer high carbon part: the addition amount of the liquid phenolic resin is 3-4% of the total mass of the outer layer composite material.
In the inner layer low carbon part: the addition amount of the liquid phenolic resin is 3-4% of the total mass of the inner layer composite material.
Further, the 99 large-crystal fused magnesia particles and the 99 large-crystal fused magnesia fine powder are as follows: mgO content is more than or equal to 99%, fe 2 O 3 The content of SiO is less than or equal to 0.2 percent 2 The content of CaO is less than or equal to 0.2 percent, and the content of CaO is less than or equal to 0.4 percent.
Further, the particle size of the 99 large-crystal fused magnesia particles comprises four types of mixture of 3-1 mm, 2-1 mm, 1-0.5 mm and 0.5-1 mm, and four types of particles are designed to be filled step by step more easily to form compact stacking, the compact stacking is conducive to forming to realize low porosity, and the integral stripping resistance of the tapping hole brick is indirectly improved.
Further, the grain size of the 99 large-crystal fused magnesia fine powder is 200 meshes.
Further, in the nano alumina powder, w (Al 2 O 3 ) 99% or more and the granularity is 50-100 μm.
Further, in the aluminum-tungsten alloy powder, W (Al+W) is more than or equal to 99 percent, and the granularity is 500 meshes.
Further, in the metal silicon powder, w (Si) is more than or equal to 99 percent, and the granularity is 400 meshes.
Further, in the boron nitride powder, w (BN) is more than or equal to 99 percent, and the granularity is less than or equal to 1 mu m. Boron nitride has chemical resistance and is not corroded by inorganic acid and water. Boron nitride starts to decompose at about 2700 ℃ under vacuum with a relative density of 2.29 and a compressive strength of 170Mpa, while boron nitride has most of its properties better than carbon materials up to 2800 ℃ under an inert reducing atmosphere: the heat-resistant and corrosion-resistant composite material has the advantages of low friction coefficient, good high-temperature stability, good heat shock resistance, high strength, high heat conductivity, low expansion coefficient and corrosion resistance.
Further, in boron carbide, B 4 The content of C is more than or equal to 95 percent, the content of B is more than or equal to 76.5 percent, the content of C is more than or equal to 20 percent, the molar hardness is 9.3, and B 4 C has a low density (2.52 g/cm) 3 ) High melting point (2450 ℃), high elastic modulus (448 GPa), low expansion coefficient (5.0X10) -6 K) and good high temperature strength, fracture toughness and chemical stability.
Further, the particle size of the flake graphite is 100 mesh, and the flake graphite comprises: the content of fixed carbon is more than or equal to 98 percent, the content of volatile matters is less than or equal to 1 percent, the content of ash is less than or equal to 1.0 percent, and the moisture is less than or equal to 0.5 percent
Further, in calcium boride, w (CaB 6 ) 99% or more and the granularity is 1-10 μm. The calcium hexaboride is black gray powder or granule. Melting point 2230 ℃ and relative density of 2.33g/cm 3 Is insoluble in water, has strong oxidation resistance, thermal shock resistance, chemical corrosion resistance and other characteristics, and has high strength and stability under thermal shock.
Further, in the asphalt powder: the content of fixed carbon is more than or equal to 60%, the content of ash is less than or equal to 0.5%, the content of volatile matters is less than or equal to 50%, the content of toluene insoluble matters is less than or equal to 24.5%, and the softening point is: 120-160 ℃.
Further, the carbon black is N330, wherein w (C) is more than or equal to 99%, and the particle size of the carbon black is 10-25 nm.
The preparation method of the low-carbon composite converter tapping hole brick comprises the following steps: preparing an outer layer composite material and an inner layer composite material according to the weight ratio respectively, uniformly preheating the prepared raw materials to 35-40 ℃, adding a molding binder, mixing at a high speed to obtain a raw material of an outer layer high carbon part and a raw material of an inner layer low carbon part, molding, forming the outer layer high carbon part and the inner layer low carbon part by high pressure molding, and sequentially drying, soaking oil, dry distilling and sand cleaning to obtain the finished product. The steel tapping hole comprises a steel tapping hole body, a working layer, a steel tapping hole body and a steel tapping layer, wherein the working layer is an inner layer low-carbon part, and the steel tapping hole body is an outer layer high-carbon part.
Further, the method comprises the following specific steps:
step one, preparing granules:
inner layer granule material: uniformly mixing 10-15 parts of 99 large-crystal fused magnesia particles 3-1 mm, 20-25 parts of 99 large-crystal fused magnesia particles 2-1 mm, 15-20 parts of 99 large-crystal fused magnesia particles 1-0.5 mm and 5-10 parts of 99 large-crystal fused magnesia particles 0.5-1 mm for 6-10 minutes by a V-shaped stirrer according to the weight ratio to obtain a steel-tapping hole brick inner layer working layer particle mixture;
outer layer granule material: according to the weight ratio, evenly mixing 5 to 10 parts of 99 large-crystal fused magnesia particles 3 to 1mm,20 to 25 parts of 99 large-crystal fused magnesia particles 2 to 1mm,10 to 15 parts of 99 large-crystal fused magnesia particles 1 to 0.5mm and 5 to 10 parts of 99 large-crystal fused magnesia particles 0.5 to 1mm for 6 to 10 minutes by a V-shaped stirrer to obtain the mixture of the inner working layer particles of the steel-tapping hole brick and the mixture of the outer body particles of the steel-tapping hole brick body.
Step two, preparing mixed powder:
inner layer powder: uniformly mixing 8-18 parts of 99 large-crystal fused magnesia fine powder, 2-10 parts of nano alumina powder, 2-4 parts of carbon black, 4-8 parts of metal aluminum tungsten alloy powder, 1-4 parts of boron nitride powder, 0.5-2 parts of boron carbide and 0.5-1 part of calcium boride in a weight ratio by a high-speed powder mixer for 13-20 minutes to obtain steel brick inner layer mixed powder additive premix powder;
and (3) outer layer powder: according to the weight ratio, 8 to 18 parts of 99 large crystal fused magnesia fine powder, 1 to 6 parts of aluminum tungsten alloy, 2 to 4 parts of metal silicon powder, 1 to 2 parts of high temperature asphalt powder and 0.5 to 2 parts of boron carbide are uniformly mixed for 13 to 20 minutes by a high-speed powder mixer to obtain the additive premix powder of the outer layer body of the tapping hole brick body.
Step three, high-speed mixing: the two prepared granules and the two mixed powder additives are preheated to 30-40 ℃ by a drying room, and then liquid thermosetting phenolic resin and solid resin powder with corresponding proportions are added by a high-speed mixing mill, and pug is fully and uniformly mixed by high-speed mixing grinding for 15-20 minutes. Wherein:
the sequence of mixing mud materials of the inner working layer of the steel brick is as follows: granule material- & gt binder (5-8 min- & gt mixed powder (10-15 min); and obtaining the mixed pug of the inner layer body of the steel brick.
The outer layer mixture of the steel brick body is mixed and ground in sequence: particle material, binder (5-8 min), 10-20 parts of graphite (3 min), and mixed powder (8-12 min); and obtaining the mixed pug of the outer layer body of the steel brick.
Step four, high-pressure forming: and D, adding the two pugs obtained in the third step into a die by using a separation sleeve according to the thickness ratio of the outer high carbon part and the inner low carbon part, extracting the sleeve according to the thickness ratio, and forming in an isostatic pressing mode to obtain a semi-finished steel tapping hole blank. The inner layer working surface is in direct contact with molten steel and is made of inner layer material, the thickness of the inner layer low carbon part accounts for 10% -40% and the thickness of the outer layer high carbon part accounts for 60% -90% in the radial direction of the steel tapping hole brick.
Step five, drying and solidifying: and (3) naturally airing the finished blank body of the tap hole obtained in the step four for 8 hours, and then drying and curing the blank body, wherein the heating speed is 10 ℃/hour, the temperature is kept at 110 ℃ for 12 hours, and the temperature is kept at 250 ℃ for 12 hours.
Step six, oil immersion: and (3) immediately carrying out oil immersion treatment on the dried tap hole bricks, wherein the surface temperature is not lower than 220 ℃, the medium is medium-temperature imported environment-friendly asphalt, and the softening point is 90 ℃. Vacuumizing to discharge air-conditioning gas in the brick body, immersing the brick body in oil at 1.5Mpa for 2-4 hours, so that the inside of the brick body is filled with asphalt.
Step seven, sand cleaning: and D, carrying out surface treatment on the steel-tapping hole brick subjected to oil immersion treatment in the step six by a shot blasting machine to obtain a finished product.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The low-carbon composite converter tapping hole brick adopts layered materials, the outer layer main body material is an outer layer high-carbon part, the carbon content is about 10% -20%, the elasticity modulus is low, and the higher graphite content is beneficial to heat conduction, so that the integral high-temperature resistance of the tapping hole is effectively enhanced; the low carbon part of the inner layer is made of a low carbon composite material, the carbon content is 3-6%, the low carbon can improve the density of the blank, the oxidation of carbon is avoided, a large number of air holes are generated in the oxidized brick, the structure is loose, and the high-temperature flexural strength is reduced;
(2) According to the invention, the carbon content of the inner layer low-carbon part material is about 3% -6%, so that the rapid change of the temperature of the tapping hole bricks before and after tapping can be reduced due to low heat conductivity of the inner layer while graphite oxidation is avoided, and the thermal shock stability of brick bodies is improved;
(3) MgO and B in the low-carbon composite converter tapping hole brick material of the invention 4 C is reduced, the reaction generates boron magnesium salt whisker, and carbon among large crystals is blocked in a bridge form, so that further oxidation is avoided. Simultaneously generated B 2 O 3 The liquid phase can isolate the contact between the oxidizing gas and the material, relieve stress concentration and improve the peeling resistance of the material.
(4) The SiO generated after the reaction of metallic silicon and oxygen in the tapping hole brick material of the low-carbon composite converter of the invention 2 Protecting the carbon from oxidation; the silicon dioxide produced simultaneously will be able to form or react to form liquid phases, and these liquid phases and B of the liquid phases 2 O 3 Likewise, pores of the material are blocked, so that the oxidation resistance of the carbonaceous material is improved;
(5) The oxidation product Al of metallic aluminum in the low-carbon composite converter tapping hole brick material of the invention 2 O 3 And MgO in the matrix to form MgO.Al 2 O 3 Spinel, mgO.Al 2 O 3 Spinel is a high-temperature bonding phase and is accompanied by volume expansion effect, so that pores and gas diffusion channels are blocked, and the oxidation resistance of the material is improved;
(6) The boron nitride powder and the metal aluminum tungsten in the low-carbon composite converter tapping hole brick material generate aluminum oxide and tungsten oxide compounds at high temperature, and simultaneously react with boron oxide in a thermosetting way at 1200-1400 ℃ under the action of nano oxidation catalysis to generate aluminum borate whisker and tungsten boride compounds, so that the bonding strength of a particle interface is enhanced, the microstructure is improved, and the wear resistance and the corrosion resistance are improved;
(7) The low-carbon composite converter tapping hole brick material adopts a vacuum pressure maintaining process of impregnating asphalt, and asphalt can effectively fill air holes among particles, and the overall density and carbon content of the tapping hole brick are increased, so that the erosion resistance and molten steel scouring resistance of the tapping hole brick are improved.
Drawings
FIG. 1 is an electron microscope image of the junction of the inner low carbon portion and the outer high carbon portion of the tap hole brick in example 1;
FIG. 2 is an electron microscope image of the junction of the inner low carbon portion and the outer high carbon portion of the tap hole brick in example 2;
FIG. 3 is an electron microscope image of the junction of the inner low carbon portion and the outer high carbon portion of the tap hole brick in example 3;
FIG. 4 is an electron microscope image of the junction of the inner low carbon portion and the outer high carbon portion of the tap hole brick in example 4.
Detailed Description
The following detailed description of exemplary embodiments of the invention, while these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. Accordingly, the scope of the invention is limited only by the attached claims.
Wherein, table 1 is a list of the components of the tapping hole brick of the low-carbon composite converter in each embodiment of the invention, and table 2 is a performance parameter of the tapping hole brick of the whisker reinforced low-carbon composite converter obtained in embodiments 1 to 4.
Table 1 list of ingredients of tap hole bricks of low carbon composite converter in each example
Example 1
The whisker reinforced low-carbon composite converter tapping hole brick and the preparation method thereof comprise the following specific steps:
step one, preparing particles: 1. according to the weight ratio, 3-1 mm of 99 large-crystallization fused magnesia particles, 2-1 mm of 11 parts of 99 large-crystallization fused magnesia particles, 1-0.5 mm of 10 parts of 99 large-crystallization fused magnesia particles and 0.5-1 mm of 12 parts of 99 large-crystallization fused magnesia particles are uniformly mixed by a V-shaped stirrer for 6-10 minutes to obtain the steel-hole brick inner layer working layer particle mixture. 2. According to the weight ratio, evenly mixing 5 parts of 99 large-crystallization fused magnesia particles 3-1 mm,21 parts of 99 large-crystallization fused magnesia particles 2-1 mm,8 parts of 99 large-crystallization fused magnesia particles 1-0.5 mm and 10 parts of 99 large-crystallization fused magnesia particles 0.5-1 mm for 6-10 minutes by a V-shaped stirrer to obtain the steel-tapping hole brick inner layer working layer particle mixture and the steel-tapping hole brick body outer layer body particle mixture.
Step two, mixed powder configuration: 1. uniformly mixing 8 parts of 99 large-crystal fused magnesia fine powder, 6 parts of nano alumina powder, 2 parts of carbon black, 4 parts of metal aluminum tungsten powder, 4 parts of boron nitride, 2 parts of boron carbide and 1 part of calcium boride in a high-speed powder mixer for 13-20 minutes according to the weight ratio to obtain additive premix powder of mixed powder of the inner layer of the steel brick; 2. according to the weight ratio, 10 parts of 99 large crystal fused magnesia fine powder, 4 parts of metal aluminum tungsten powder, 2 parts of metal silicon powder, 1 part of boron carbide and 1 part of asphalt powder are uniformly mixed by a high-speed powder mixer for 13-20 minutes to obtain the additive premix powder of the outer layer body of the tapping hole brick body.
Step three, high-speed mixing: the two prepared granules and the two mixed powder additives are preheated to 30-40 ℃ through a drying room, then liquid thermosetting phenolic resin and solid resin powder with corresponding weight percentages are added by a high-speed mixing mill, and pugs are fully and uniformly mixed after being mixed and ground for 15-20 minutes at a high speed. The sequence of mixing mud materials of the inner working layer of the steel brick is as follows: particles- & gt binder (5-8 min- & gt mixed powder (10-15 min); obtaining the mixed pug of the outer layer body of the steel brick. The outer layer mixture of the steel brick body is mixed and ground in sequence: particles, binding agent (5-8 minutes), 15 parts of graphite (3 minutes), and mixed powder (8-12 minutes); and obtaining the mixed pug of the outer layer body of the steel brick.
Step four, high-pressure forming: and D, adding the two pugs obtained in the third step into a die by using a separation sleeve according to the composite proportion, extracting the sleeve according to the composite proportion, and forming in an isostatic pressing mode to obtain a semi-finished steel tapping hole blank. The inner layer working surface is in direct contact with molten steel and is an inner layer material, and the thickness of the outer layer high carbon part in the radial direction of the steel tapping hole brick accounts for 90 percent; the thickness of the inner layer low carbon portion was 10%. It is worth to say that, because the binder of the inner and outer layers adopts phenolic resin as well, the two raw material systems are basically consistent, namely, the grains adopt magnesia, the fine powder adopts different antioxidants, and the two materials can be basically combined together in percentage by high pressure during molding, so that the problem of delamination or unstable combination of the actual product does not exist.
Step five, drying and solidifying: and (3) naturally airing the finished blank body of the tap hole obtained in the step four for 8 hours, and then drying and curing the blank body, wherein the heating speed is 10 ℃/hour, the temperature is kept at 110 ℃ for 12 hours, and the temperature is kept at 250 ℃ for 12 hours.
Step six, oil immersion: and (3) immediately carrying out oil immersion treatment on the dried tap hole bricks, wherein the surface temperature is not lower than 220 ℃, the medium is medium-temperature imported environment-friendly asphalt, and the softening point is 90 ℃. And (3) vacuumizing, and then immersing in oil and maintaining the pressure for 2-4 hours.
Step seven, sand cleaning: and D, carrying out surface treatment on the steel-tapping hole brick subjected to oil immersion treatment in the step six by a shot blasting machine to obtain a finished product.
Example 2
In the whisker reinforced low-carbon composite converter tapping hole brick, the thickness ratio of the outer layer high-carbon part is 80%; the inner layer low carbon portion was 20% in thickness, and its composition and mass fraction were as shown in Table 1, and the preparation method was the same as in example 1.
Example 3
In the whisker reinforced low-carbon composite converter tapping hole brick, the thickness ratio of the outer layer high-carbon part is 70%; the thickness ratio of the inner layer low carbon portion was 30%, and the composition and mass fraction thereof were as shown in Table 1, and the preparation method was the same as in example 1.
Example 4
In the whisker reinforced low-carbon composite converter tapping hole brick, the thickness ratio of the outer layer high-carbon part is 60%; the inner layer low carbon portion was 40% in thickness, and its composition and mass fraction were as shown in Table 1, and the preparation method was the same as in example 1.
Table 2 Performance of the Low carbon composite converter tap hole brick obtained in examples 1 to 4 and service life of certain Steel works
The carbon content in table 2 is detected by using a GB/T16555-2017 carbon-containing refractory material high-frequency furnace combustion infrared absorption method, namely, carbon in various chemical forms in a sample is combusted in an oxygen flow to be converted into carbon dioxide, the produced carbon dioxide is carried by oxygen to a measuring chamber for infrared absorption detection, the carbon dioxide absorbs infrared energy with specific wavelength, the absorption energy is in direct proportion to the carbon concentration, and the total carbon content of the sample is measured according to the energy change received by a detector.
Fig. 1 to 4 are respectively electron microscope images of the junction between the inner layer and the outer layer in the sections of the tap hole bricks in examples 1 to 4, large crystallized magnesia which can be observed on the surface exists in a block form, the rest of fine powder matrixes are uniformly distributed, and meanwhile, the junction between the inner layer and the outer layer is better, and no crack penetrates and breaks.
The whisker reinforced low-carbon composite converter tapping hole brick is tried out on a converter in a steel mill, and smelting conditions in the steel mill are as follows: 150t of the converter, about 160t of actual tapping quantity, 1660-1680 ℃ of tapping temperature of molten steel, and 6 minutes of tapping time average, mainly smelting alloy steel such as manganese steel, chromium steel and the like, wherein the service life of the original tapping hole is about 190, and 265-290 times of the service life of the tapping hole of the low-carbon composite converter is reinforced by using test whiskers at present, so that the steelmaking benefit of the converter is greatly improved.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The utility model provides a low carbon composite converter tapping hole brick which characterized in that: the radial direction comprises an outer layer high carbon part and an inner layer low carbon part from outside to inside, wherein the carbon content of the outer layer high carbon part is 10% -20%, and the carbon content of the inner layer low carbon part is 3% -6%.
2. The low-carbon composite converter tap hole brick according to claim 1, wherein: the thickness of the outer layer high carbon part in the radial direction of the steel tapping hole brick accounts for 60% -90%; the thickness of the inner layer low carbon part accounts for 10-40%.
3. The low-carbon composite converter tap hole brick according to claim 1, wherein: the raw material composition of the outer layer high carbon part and the raw material composition of the inner layer low carbon part both contain MgO and B 4 C。
4. A low carbon composite converter tap hole brick according to claim 3, wherein: the outer layer high carbon part is composed of an outer layer composite material and a forming binder, wherein the outer layer composite material comprises the following raw materials in parts by weight:
5. a low carbon composite converter tap hole brick according to claim 3, wherein: the inner layer low-carbon part is composed of an inner layer composite material and a forming binder, wherein the inner layer composite material comprises the following raw materials in parts by weight:
6. a low carbon composite converter tap hole brick according to claim 4 or 5, wherein: the molding binder comprises liquid phenolic resin and solid phenolic resin powder, wherein the addition amount of the liquid phenolic resin is 3-4% of the total mass of the outer layer composite material or the inner layer composite material.
7. A low carbon composite converter tap hole brick according to claim 4 or 5, wherein: the grain size of the 99 large crystal fused magnesia grain comprises four kinds of mixture of 3-1 mm, 2-1 mm, 1-0.5 mm and 0.5-1 mm.
8. A low carbon composite converter tap hole brick according to claim 4 or 5, wherein: the grain size of the 99 large-crystal fused magnesia fine powder is 200 meshes.
9. A low carbon composite converter tap hole brick according to claim 4 or 5, wherein: boron carbide, B 4 The content of C is more than or equal to 95%, the content of B is more than or equal to 76.5%, the content of C is more than or equal to 20%, the Mohs hardness is 9.3, and the relative density is 2.52g/cm 3 The melting point is 2450 ℃, the elastic modulus is 448GPa, and the expansion coefficient is 5.0x10 -6 /K。
10. A method for preparing the low-carbon composite converter tapping hole brick according to any one of claims 1-9, which is characterized in that: the method comprises the following steps: respectively preparing raw materials of an outer high-carbon part and an inner low-carbon part after high-speed mixing, forming the outer high-carbon part and the inner low-carbon part by high-pressure molding after die filling, and then sequentially drying, soaking oil, dry distillation and sand removal to obtain a finished product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117069480A (en) * | 2023-08-15 | 2023-11-17 | 大石桥市冠诚耐火材料有限公司 | Low-carbon magnesia carbon brick for producing stainless steel by converter and preparation process thereof |
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| JPH04338162A (en) * | 1991-05-08 | 1992-11-25 | Sumitomo Metal Ind Ltd | Magnesia-carbon brick having multilayered structure |
| KR19980052564A (en) * | 1996-12-24 | 1998-09-25 | 서상기 | Magnesia-silicon carbide-carbon yeonwa for converter |
| JP2014091633A (en) * | 2012-10-31 | 2014-05-19 | Kurosaki Harima Corp | Carbon-containing brick |
| CN210151147U (en) * | 2019-03-29 | 2020-03-17 | 浙江宏丰炉料有限公司 | Thermal shock resistant magnesia carbon brick for converter trunnion |
| CN112608135A (en) * | 2020-12-30 | 2021-04-06 | 马鞍山利尔开元新材料有限公司 | Low-cost magnesia-zirconia-carbon converter steel-tapping hole brick and preparation method thereof |
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2023
- 2023-01-28 CN CN202310104107.XA patent/CN116287534A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04338162A (en) * | 1991-05-08 | 1992-11-25 | Sumitomo Metal Ind Ltd | Magnesia-carbon brick having multilayered structure |
| KR19980052564A (en) * | 1996-12-24 | 1998-09-25 | 서상기 | Magnesia-silicon carbide-carbon yeonwa for converter |
| JP2014091633A (en) * | 2012-10-31 | 2014-05-19 | Kurosaki Harima Corp | Carbon-containing brick |
| CN210151147U (en) * | 2019-03-29 | 2020-03-17 | 浙江宏丰炉料有限公司 | Thermal shock resistant magnesia carbon brick for converter trunnion |
| CN112608135A (en) * | 2020-12-30 | 2021-04-06 | 马鞍山利尔开元新材料有限公司 | Low-cost magnesia-zirconia-carbon converter steel-tapping hole brick and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117069480A (en) * | 2023-08-15 | 2023-11-17 | 大石桥市冠诚耐火材料有限公司 | Low-carbon magnesia carbon brick for producing stainless steel by converter and preparation process thereof |
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