CN117923879A - Slag line brick, preparation method thereof and application thereof to steel ladle - Google Patents
Slag line brick, preparation method thereof and application thereof to steel ladle Download PDFInfo
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- CN117923879A CN117923879A CN202410095503.5A CN202410095503A CN117923879A CN 117923879 A CN117923879 A CN 117923879A CN 202410095503 A CN202410095503 A CN 202410095503A CN 117923879 A CN117923879 A CN 117923879A
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- 239000011449 brick Substances 0.000 title claims abstract description 115
- 239000002893 slag Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 title description 8
- 239000010959 steel Substances 0.000 title description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 aluminum magnesium carbon Chemical compound 0.000 claims abstract description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 229910018134 Al-Mg Inorganic materials 0.000 claims abstract description 11
- 229910018467 Al—Mg Inorganic materials 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 4
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 239000011819 refractory material Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 19
- 238000010009 beating Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000009273 molten salt oxidation Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007767 bonding agent Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
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- 230000009466 transformation Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
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- 230000008646 thermal stress Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a slag line brick, a preparation method thereof and application thereof to a ladle, and belongs to the technical field of refractory materials. 1. The material comprises the following components in parts by weight: 5-0mm of regenerated magnesium carbon particles: 45-60 parts; 5-1mm of regenerated aluminum magnesium carbon particles: 10-15 parts of a lubricant; 96.3 magnesia with the diameter of 1-0 mm: 5-15 parts; 200 mesh 96.3 magnesite: 15-22 parts of a lubricant; graphite: 5-10 parts; a composite binder consisting of 0.1-0.2 parts of ethylene glycol and 1.9-3.8 parts of phenolic resin; a composite additive consisting of 2.5-5 parts of Al-Mg alloy and 0.5-1 part of B 4 C. The invention adopts the regenerated material, realizes the recycling of resources, and simultaneously responds to the national policies about recycling of resources and green production; and the performance of the product can be improved with lower cost, and the great reduction of the overall performance of the ladle brick caused by the change of materials is reduced.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a slag line brick, a preparation method thereof and application thereof to a ladle.
Background
The ladle has the main function of transferring molten steel when steelmaking is started, and is connected with a converter, an electric furnace and continuous casting. However, with the development of the age, the components, the temperature and the like of molten steel are required to be accurately controlled, the main functions of the ladle are further enhanced, and the ladle is developed into main equipment for external refining; as shown in figure 1, the ladle slag line brick is particularly important as an important component of a ladle, the slag system adopted in the slag making process is CaO-SiO 2-Al2O3 -MgO slag system, the deoxidizing element adopts Al or Si, a certain amount of high-alumina slag is added, and the magnesia carbon brick is used as a slag line.
According to the information known at present, chinese patent publication No. CN110451932A discloses a ladle slag line magnesia carbon brick, which tightly combines magnesia aggregate particles with crystalline flake graphite, enhances the ceramic combination of a material matrix, improves the material organization structure, and further improves the strength. Chinese patent publication No. CN114751757A discloses a long-life ladle slag line brick which is made of an electric smelting magnesia material, an electric smelting calcium zirconate material, an electric smelting monoclinic zirconia material and the like, and has good erosion resistance when being used as the ladle slag line brick under the refining conditions of a long-time LF furnace and a VD furnace. Chinese patent publication No. CN107352977a discloses a slag line brick for ladle, which adopts phenolic resin with better wettability and moisture retention, increases critical particle size, properly controls the addition amount of metal or alloy powder, improves the addition amount of graphite, introduces micro-additives, buffers thermal stress, and improves thermal shock stability of slag line brick. Chinese patent publication No. CN110143807a discloses a metal composite low-carbon magnesia carbon brick for ladle slag line, which adopts natural crystalline flake graphite, expanded graphite, etc. The oxidation resistance and the slag resistance of the magnesia carbon brick are enhanced, and the service life of the magnesia carbon brick is greatly prolonged compared with the prior slag line magnesia carbon brick. Chinese patent publication No. CN109095896a discloses a ladle slag line brick of waste immersed nozzle slag line material pug, the main component of the immersed nozzle slag line part is zirconia, which can greatly improve the slag erosion resistance and the spalling resistance of the slag line brick. The Chinese patent publication No. CN106365617A, publication day 2017-02-01, discloses an antioxidation regenerated magnesia carbon brick for slag line parts, and the antioxidation and rapid heating resistance of the magnesia carbon brick are greatly improved through the proportion and granularity selection of the raw materials and the preparation process.
However, with the development of the national steelmaking industry, the shortage of refractory materials and the implementation of national environmental protection policies, the reuse of post-consumer refractory materials is becoming more and more important. Especially, the utilization rate of the refractory materials after the current use in China is very low and is less than 20 percent. In response to national policies, many businesses and research institutions now actively practice the recycling research and application of post-consumer refractory materials in an effort to enhance the recycling of refractory materials.
The following are the patent documents that are relevant to the search:
Patent document 1: patent publication No. CN106278329A discloses a regenerated magnesia carbon brick for slag line position, 30-40 parts of regenerated material with granularity smaller than 1mm are added, and the oxidation resistance and the rapid cooling and rapid heating resistance of the magnesia carbon brick are improved through the proportion and granularity selection of the raw materials and the preparation process, so that the service life of the ladle is prolonged.
Patent document 2: patent publication No. CN105622070A discloses a magnesia carbon brick prepared by using magnesia carbon residual bricks, which takes electric fused magnesia and magnesia carbon residual bricks (magnesia carbon residual brick particles: 40-60 parts) with different particle grades as main raw materials, takes phenolic resin as a binding agent, and fully utilizes secondary resources of the magnesia carbon residual bricks by adding a composite additive.
However, the above-mentioned patent does not achieve good performance in actual use after adding the regenerated magnesia carbon bricks, and particularly has unsatisfactory aggressiveness and oxidation resistance.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the aggressiveness or oxidation resistance of slag line bricks are not ideal due to the use of reclaimed materials in the prior art, the invention provides the slag line bricks, which at least can improve the aggressiveness and ensure the use safety of the slag line bricks.
The invention further aims at providing a preparation method of the slag line brick.
The invention further aims to provide an application of the slag line brick to a ladle.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a slag line brick, which comprises the following components in parts by weight:
5-0mm of regenerated magnesium carbon particles: 45-60 parts;
5-1mm of regenerated aluminum magnesium carbon particles: 10-15 parts of a lubricant;
96.3 electric smelting magnesia with the diameter of 1-0 mm: 5-15 parts;
200 mesh 96.3 electric smelting magnesite: 15-22 parts of a lubricant;
Graphite: 5-10 parts;
The composite bonding agent consists of 0.1-0.2 part of ethylene glycol and 1.9-3.8 parts of phenolic resin (the proportion of the phenolic resin to the ethylene glycol is 19:1), so that the wettability of the pug is better, and the addition amount of the phenolic resin is reduced;
the composite additive consisting of 2.5-5 parts of Al-Mg alloy and 0.5-1 part of B 4 C (the ratio of the Al-Mg alloy to the B4C is 5:1) improves the oxidation resistance and the erosion resistance of the ladle brick.
According to any one of the first aspect of the object of the present invention, the 5-0mm regenerated magnesium carbon particle size comprises a mixture of four of 5-3mm, 3-1mm, 1-0.5mm, and 0.5-0mm, wherein the mass fraction of each particle size is:
According to any one of the first embodiment of the object of the present invention, the particle size of the 5-1mm regenerated aluminum magnesium carbon particles comprises a mixture of 5-3mm and 3-1mm, wherein the mass fraction of each particle size is as follows:
5-10 parts of 5-3mm regenerated aluminum magnesium carbon material;
5-10 parts of 3-1mm regenerated aluminum magnesium carbon material.
According to any one of the first aspect of the object of the present invention, the 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm regenerated magnesium-carbon particles are obtained by mixing and grinding and then sieving, and then the 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm particles are subjected to molten salt oxidation treatment.
According to any one of the first aspect of the object of the present invention, the salt in the molten salt oxidation is one or more of sodium carbonate and potassium carbonate.
According to any one of the first embodiment of the object of the invention, the 5-3mm and 3-1mm regenerated aluminum magnesium carbon particles are obtained by sieving after mixing and grinding, and then the 5-3mm and 3-1mm particles are subjected to molten salt oxidation treatment.
According to any one of the first aspect of the object of the present invention, the salt in the molten salt oxidation is one or more of sodium carbonate and potassium carbonate.
The second aspect of the invention provides a method for preparing slag line bricks, comprising the following steps: the slag line brick is prepared from granular aggregate (comprising 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm, 1-0mm of regenerated magnesium carbon material, 5-3mm, 3-1mm of regenerated aluminum magnesium carbon material, 1-0mm of 96.3 fused magnesia,) →60wt% of binding agent→graphite→magnesia fine powder (200 meshes of 96.3 fused magnesia) →40wt% of binding agent→additive→discharging→molding→heat treatment→finished product in the above manner; the steps are all the prior art, but note that after the graphite is added, the magnesia fine powder is added after premixing for 3 minutes, so that the molding is convenient; the total mixing time is not less than 25min, preferably 25-30min.
The third aspect of the invention provides an application of the slag line brick of the first aspect or the preparation method of the second aspect to steel ladles.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the slag line brick adopts the regenerated magnesia-alumina-carbon bricks and magnesia-carbon bricks as main raw materials, and the regenerated materials mainly come from waste refractory materials, such as waste magnesia-alumina-carbon bricks, magnesia-carbon bricks and the like; the materials are crushed, ground, screened and the like to obtain regenerated raw materials with moderate granularity; the recycled material can greatly reduce the production cost of ladle slag line bricks, and is also beneficial to the reasonable utilization and environmental protection of resource conservation; the binding agent and the additive are optimally researched and developed, the binding agent is used as an adhesive between materials, plays a role in connecting each particle and enhancing structural stability, and the additive is used as a flavoring agent between materials, so that the overall performance of the refractory brick is directly influenced; the novel composite binding agent and additive have good erosion resistance so as to ensure the safety of the ladle slag line brick in the use process.
Drawings
The technical solution of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for the purpose of illustration only and thus are not limiting the scope of the present invention. Moreover, unless specifically indicated otherwise, the drawings are intended to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.
Fig. 1 is a schematic structural view of a ladle to which the slag line brick of the present invention is applied.
Detailed Description
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.
[ Slag line brick ]
The ladle slag line brick comprises the following components in parts by weight: 5-0mm of regenerated magnesium carbon particles: 45-60 parts; 5-1mm of regenerated aluminum magnesium carbon particles: 10-15 parts of a lubricant; 1-0mm of 96.3 electro-fused magnesia (96.3 represents purity): 5-15 parts; 200 mesh 96.3 fused magnesia (96.3 represents purity): 15-22 parts of a lubricant; graphite: 5-10 parts; the composite bonding agent consists of 0.1-0.2 part of ethylene glycol and 1.9-3.8 parts of phenolic resin (the proportion of the phenolic resin to the ethylene glycol is 19:1), so that the wettability of the pug is better, and the addition amount of the phenolic resin is reduced; the composite additive consists of 2.5-5 parts of Al-Mg alloy and 0.5-1 part of B 4 C (the ratio of the Al-Mg alloy to the B 4 C is 5:1), so that the oxidation resistance and erosion resistance of the ladle brick are improved.
1) Regenerated magnesium carbon particles: the particle size of the 5-0mm regenerated magnesium carbon particles comprises a mixture of 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm, wherein the mass parts of the particle sizes are as follows:
The particle size distribution adopts frequency distribution and accumulation distribution, so that the particle size of the regenerated magnesium carbon particles comprises four frequency distributions of 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm, which are respectively expressed as follows: 3<X is less than or equal to 5;1<X is less than or equal to 3; x is more than or equal to 0.5 and less than or equal to 1, 0<X is more than or equal to 0.5.
2) Regenerated aluminum magnesium carbon particles: the particle size of the regenerated aluminum magnesium carbon particles comprises a mixture of 5-3mm and 3-1mm, wherein the mass parts of each particle size are as follows:
5-10 parts of 5-3mm regenerated aluminum magnesium carbon material;
5-10 parts of 3-1mm regenerated aluminum magnesium carbon material.
The particle size distribution adopts frequency distribution and accumulation distribution, so that the particle size of the regenerated aluminum magnesium carbon particles comprises two frequency distributions of 5-3mm and 3-1mm, which are respectively expressed as follows: 3<X is less than or equal to 5;1<X is less than or equal to 3.
However, recycling of waste magnesia carbon bricks and alumina magnesia carbon bricks causes several problems; 1) Organic solvents (including resin and other organic compounds) in the waste magnesia carbon bricks and the aluminum magnesia carbon bricks are in a low-melting phase in the high-temperature use process, so that the perforation is very easy to cause, the erosion of molten steel to slag line bricks is increased, and meanwhile, the slag line bricks are heated to easily generate cracks along the perforation edges, so that the cracking problem of the slag line bricks is accelerated; 2) The waste magnesia carbon bricks and the aluminum magnesia carbon bricks are broken, and the original binding agent binds the particle materials together to form false particles, so that the false particles have low strength, are extremely easy to crack after being heated, and bring potential safety hazards to the use of slag line bricks.
Pretreatment of regenerated magnesium carbon particles
Binder (phenolic resin) and other organic compounds are present in the spent magnesia carbon bricks, and the regenerated magnesia carbon particles can be pretreated during the regeneration process. The regenerated magnesium carbon particles are firstly mixed and ground, then screened, and then the particles with the particle diameters of 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm are subjected to molten salt oxidation treatment; the salt in the molten salt oxidation is sodium carbonate or potassium carbonate or sodium carbonate and potassium carbonate, and any proportion of the two can be adopted for the mixture.
Because the adding proportion of each granularity of the reclaimed materials has great influence on the volume density, the apparent porosity and the compressive strength of the ladle slag line brick and the quantity of the pseudo particles in the reclaimed materials has great influence on the physical properties, the proportion of each granularity of the reclaimed materials needs to be adjusted, and the reclaimed materials are obtained by optimizing:
Step one, mixing and grinding: after the waste bricks are crushed into particles smaller than 50mm, the particles are put into a sand mixer for stirring, so that aggregates and matrixes in the waste bricks are easy to separate in the rolling process, the generation of false particles is reduced, and the semi-finished products are prevented from swelling and cracking during heat treatment; rolling treatment is carried out after the trapped materials are stirred for more than or equal to 24 hours, and after the treatment, the proportion of pseudo particles in particles with the diameter of more than 1mm can be controlled within 10 weight percent, and the proportion of pseudo particles in particles with the diameter of less than or equal to 1mm is more and is not less than 20 weight percent;
And secondly, molten salt treatment: the specific molten salt treatment process comprises the following steps: adding molten salt substances into regenerated magnesium carbon particles with the weight of 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm, wherein the adding amount is 0.5-1.0% of the weight of the regenerated magnesium carbon particles, stirring and mixing, keeping the temperature of a horse boiling furnace or an incinerator at 850-900 ℃ for 20min, specifically 850 ℃, 855 ℃, 860 ℃, 865 ℃, 870 ℃, 875 ℃, 880 ℃, 890 ℃, 895 ℃ and 900 ℃, preferably 850-870 ℃, 855 ℃, 860 ℃, 865 ℃ and 870 ℃, cooling to room temperature, cleaning by ultrasonic waves, adding water (prior art), and drying at 110 ℃, and in the process, finding that water can promote hydration of Al 4C3 in waste materials, thereby further solving the problem of expansion caused by absorbing water vapor in the air in the use process of slag line bricks.
The specific analysis of the pretreatment process is as follows: direct oxidation and molten salt oxidation of binders (phenolic resins) and other organic compounds are divided into three phases: the first stage: a heating process at 25-200deg.C; and a second stage: a rapid thermal decomposition stage at 200-450 ℃; and a third stage: and (3) a continuous oxidation stage at 450-870 ℃.
Through analysis of the process, the inventor surprisingly finds that resin and organic compound residues in the waste magnesia carbon bricks are almost zero, and molten salt residues are not found on the surfaces of particles, so that molten salt residues are avoided, low-temperature eutectic (particularly sodium-potassium eutectic) is generated when the slag line bricks are used at high temperature (the temperature of molten steel is about 1500 ℃, the slag line bricks are in contact with air at the temperature, and a strong oxidation reaction is generated), and the safe use performance of the slag line bricks is ensured.
The possible reasons for analyzing the above generation are: 1) The carbonate radical in the molten salt substance can generate peroxy radical and superoxide radical by contacting with dissolved oxygen, has stronger oxidizing capability, promotes the transformation of residual resin and other organic compounds in waste magnesia carbon bricks, and enables the resin network structures such as false particles and the like to be broken; 2) Ultrasonic cleaning and water adding are adopted to quickly clean molten salt substances (sodium carbonate and potassium carbonate) so that molten salt is not adhered to the surfaces of particles and is not brought into slag line bricks.
Pretreatment of the regenerated aluminum-magnesium-carbon particles
The regenerated aluminum magnesium carbon particles are firstly mixed and ground, then screened, and then the particles with the size of 5-3mm and 3-1mm are subjected to molten salt oxidation treatment, wherein the salts in the molten salt oxidation are sodium carbonate or potassium carbonate or sodium carbonate and potassium carbonate, and the mixture of the two can be matched in any proportion.
The specific molten salt treatment process comprises the following steps: adding molten salt substances into 5-3mm and 3-1mm regenerated aluminum magnesium carbon particles, wherein the adding amount is 0.5-1.0% of the weight of the regenerated aluminum magnesium carbon particles, stirring and mixing, keeping the mixture at 850-900 ℃ for 20min by adopting a horse boiling furnace or an incinerator, specifically 850 ℃, 855 ℃, 860 ℃, 865 ℃, 870 ℃, 875 ℃, 880 ℃, 890 ℃, 895 ℃ and 900 ℃, preferably 850-870 ℃, specifically 850 ℃, 855 ℃, 860 ℃, 865 ℃ and 870 ℃, then cooling to room temperature, cleaning by adopting ultrasonic waves, adding water (the prior art), and drying at 110 ℃.
The specific analysis of the pretreatment process is as follows: direct oxidation and molten salt oxidation of binders (phenolic resins) and other organic compounds are divided into three phases: the first stage: a heating process at 25-200deg.C; and a second stage: a rapid thermal decomposition stage at 200-450 ℃; and a third stage: and (3) a continuous oxidation stage at 450-870 ℃.
Through analysis of the process, the inventor surprisingly finds that resin and organic compound residues in the waste aluminum-magnesium-carbon bricks are almost zero, and molten salt residues are not found on the surfaces of particles, so that molten salt residues are avoided, low-temperature eutectic (particularly sodium-potassium eutectic) is generated when the slag line bricks are used at high temperature (the temperature of molten steel is about 1500 ℃, the slag line bricks are in contact with air at the temperature to generate strong oxidation reaction), and the safe use performance of the slag line bricks is ensured.
The possible reasons for analyzing the above generation are: 1) The carbonate radical in the molten salt substance can generate peroxy radical and superoxide radical by contacting with dissolved oxygen, has stronger oxidizing capability, promotes the transformation of residual resin and other organic compounds in the waste aluminum-magnesium-carbon brick, and breaks the resin network structures such as false particles and the like; 2) Ultrasonic cleaning and water adding are adopted to quickly clean molten salt substances (sodium carbonate and potassium carbonate) so that molten salt is not adhered to the surfaces of particles and is not brought into slag line bricks.
The preparation method of the slag line brick comprises the following steps: the slag line brick is prepared from granular aggregate (comprising 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm of regenerated magnesium carbon material, 5-3mm, 3-1mm of regenerated aluminum magnesium carbon material and 1-0mm of 96.3 fused magnesia), 60wt% of bonding agent, graphite, magnesia fine powder (200 meshes of 96.3 fused magnesia), 40wt% of bonding agent, additive, discharging, molding, heat treatment and finished product in the above manner; however, it should be noted that after the graphite is added, the magnesia fine powder is added after premixing for 3-5 minutes, so that the molding is facilitated; the total mixing time is not less than 25 minutes.
The method comprises the following specific steps:
(1) Premixing the granular aggregate: 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm and 1-0mm of regenerated magnesium carbon material in parts by weight; 5-3mm and 3-1mm of regenerated aluminum magnesium carbon material; 1-0mm of 96.3 electric smelting magnesia, 60 weight percent of binder is premixed according to parts by weight, and the mixing time is 20-30min;
(2) Mixing and grinding: adding graphite in parts by weight for premixing for 3-5 minutes, adding magnesia fine powder, adding 40wt% of binding agent in parts by weight and additives in parts by weight for continuous mixing and grinding for 25-30 minutes, preferably 25 minutes, and trapping the mud after mixing and grinding for 12-24 hours;
(3) And (5) mechanically pressing and forming: adding the pug trapped in the step (2) into a forming die for forming, lightly beating for 2-3 times, then demolding, hanging and beating for 2 times, and then gradually increasing the pressure to beat for 5-8 times, wherein the total beating times are not less than 10 times, so as to obtain a semi-finished brick blank;
(4) Baking and drying: and (3) drying the semi-finished brick blank prepared in the step (3), and preserving the heat for 15-20 hours at the drying temperature of 210+/-10 ℃.
Example 1
The ladle slag line brick comprises the following components in percentage by weight: 15 parts of 5-3mm regenerated magnesium carbon material; 20 parts of 3-1mm regenerated magnesium carbon material; 10 parts of 1-0.5mm regenerated magnesium carbon material; 5 parts of 0.5-0mm regenerated magnesium carbon material; 10 parts of 5-3mm regenerated aluminum magnesium carbon material; 5 parts of 3-1mm regenerated aluminum magnesium carbon material; 10 parts of 1-0mm 96.3 fused magnesia, 15 parts of 96.3 fused magnesia fine powder; 8 parts of graphite; and (3) a composite binding agent: ethylene glycol 0.1 part, phenolic resin: 1.9 parts of a composite additive: 2.5 parts of Al-Mg alloy and 0.5 part of B 4 C.
The concrete preparation method of the ladle slag line brick comprises the following steps:
(1) Premixing the granular aggregate: 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm and 1-0mm of regenerated magnesium carbon material in parts by weight; 5-3mm and 3-1mm of regenerated aluminum magnesium carbon material; 1-0mm of 96.3 electric smelting magnesia, 60 weight percent of binder is premixed according to parts by weight, and the mixing time is 30min;
(2) Mixing and grinding: adding graphite in parts by weight, premixing for 5 minutes, adding magnesia fine powder, adding 40wt% of binding agent in parts by weight and additives in parts by weight, continuously mixing and grinding for 25 hours, and trapping the mud after mixing and grinding for 24 hours;
(3) And (5) mechanically pressing and forming: adding the pug trapped in the step (2) into a forming die for forming, lightly beating for 3 times, then demolding, hanging and beating for 2 times, and then gradually increasing the pressure and beating again for 8 times, wherein the total beating times are 12 times, so as to obtain a semi-finished green brick;
(4) Baking and drying: and (3) drying the semi-finished green brick prepared in the step (3), and preserving the heat for 20 hours at the drying temperature of 210+/-10 ℃.
Example 2
The ladle slag line brick comprises the following components in percentage by weight: 10 parts of regenerated magnesium carbon material with the diameter of 5-3 mm; 10 parts of 3-1mm regenerated magnesium carbon material; 15 parts of 1-0.5mm regenerated magnesium carbon material; 10 parts of 0.5-0mm regenerated magnesium carbon material; 5 parts of 5-3mm regenerated aluminum magnesium carbon material; 8 parts of 3-1mm regenerated aluminum magnesium carbon material; 1-0mm of 5 parts of 96.3 fused magnesia, and 22 parts of 200-mesh 96.3 fused magnesia fine powder; 5 parts of graphite; and (3) a composite binding agent: 0.15 part of ethylene glycol, 2.85 parts of phenolic resin and composite additive: al-Mg alloy: 2.5 parts, B 4 C:0.5 part.
The concrete preparation method of the ladle slag line brick comprises the following steps:
(1) Premixing the granular aggregate: 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm and 1-0mm of regenerated magnesium carbon material in parts by weight; 5-3mm and 3-1mm of regenerated aluminum magnesium carbon material; 1-0mm of 96.3 electric smelting magnesia, 60 weight percent of binder is premixed according to parts by weight, and the mixing time is 20min;
(2) Mixing and grinding: adding graphite in parts by weight, premixing for 3 minutes, adding magnesia fine powder, adding 40wt% of binding agent in parts by weight and additives in parts by weight, continuously mixing and grinding for 30 minutes, and trapping the ground pug for 15 hours;
(3) And (5) mechanically pressing and forming: adding the pug trapped in the step (2) into a forming die for forming, lightly beating for 2 times, then demolding, hanging and beating for 2 times, and then gradually increasing the pressure and beating for 5 times, wherein the total beating times are 15 times, so as to obtain a semi-finished green brick;
(4) Baking and drying: and (3) drying the semi-finished brick blank prepared in the step (3), and preserving heat for 15h at the drying temperature of 210+/-10 ℃.
Example 3
The ladle slag line brick comprises the following components in percentage by weight: 15 parts of 5-3mm regenerated magnesium carbon material; 20 parts of 3-1mm regenerated magnesium carbon material; 10 parts of 1-0.5mm regenerated magnesium carbon material; 5 parts of 0.5-0mm regenerated magnesium carbon material; 5 parts of 5-3mm regenerated aluminum magnesium carbon material; 5 parts of 3-1mm regenerated aluminum magnesium carbon material; 10 parts of 1-0mm 96.3 fused magnesia, 18 parts of 200-mesh 96.3 fused magnesia fine powder; 8 parts of graphite; and (3) a composite binding agent: 0.2 part of ethylene glycol, 3.8 parts of phenolic resin and composite additive: 5 parts of Al-Mg alloy and 1 part of B 4 C.
The concrete preparation method of the ladle slag line brick comprises the following steps:
(1) Premixing the granular aggregate: 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm and 1-0mm of regenerated magnesium carbon material in parts by weight; 5-3mm and 3-1mm of regenerated aluminum magnesium carbon material; 1-0mm of 96.3 electric smelting magnesia, 60 weight percent of binder is premixed according to parts by weight, and the mixing time is 25 minutes;
(2) Mixing and grinding: adding graphite in parts by weight, premixing for 3-5 minutes, adding magnesia fine powder, adding 40wt% of binding agent in parts by weight and additives in parts by weight, continuously mixing and grinding for 26 minutes, and trapping the ground pug for 12 hours;
(3) And (5) mechanically pressing and forming: adding the pug trapped in the step (2) into a forming die for forming, lightly beating for 3 times, then demolding, lifting and exhausting for 2 times, gradually increasing the pressure and beating again for 8 times, and obtaining a semi-finished green brick after 10 times of total beating times;
(4) Baking and drying: and (3) drying the semi-finished green brick prepared in the step (3), and preserving the heat for 18 hours at the drying temperature of 210+/-10 ℃.
Example 4
The ladle slag line brick comprises the following components in percentage by weight: 15 parts of 5-3mm regenerated magnesium carbon material; 25 parts of 3-1mm regenerated magnesium carbon material; 10 parts of 1-0.5mm regenerated magnesium carbon material; 10 parts of 0.5-0mm regenerated magnesium carbon material; 10 parts of 5-3mm regenerated aluminum magnesium carbon material; 5 parts of 3-1mm regenerated aluminum magnesium carbon material; 15 parts of 1-0mm 96.3 fused magnesia, 20 parts of 200-mesh 96.3 fused magnesia fine powder; 10 parts of graphite; and (3) a composite binding agent: 0.1 part of ethylene glycol, 1.9 parts of phenolic resin and composite additive: 0.5 part of Al-Mg alloy and 2.5 parts of B 4 C.
The concrete preparation method of the ladle slag line brick comprises the following steps:
(1) Premixing the granular aggregate: 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm and 1-0mm of regenerated magnesium carbon material in parts by weight; 5-3mm and 3-1mm of regenerated aluminum magnesium carbon material; 1-0mm of 96.3 electric smelting magnesia, 60 weight percent of binder is premixed according to parts by weight, and the mixing time is 30min;
(2) Mixing and grinding: adding graphite in parts by weight, premixing for 5 minutes, adding magnesia fine powder, adding 40wt% of binding agent in parts by weight and additives in parts by weight, continuously mixing and grinding for 30 minutes, and trapping the ground pug for 20 hours;
(3) And (5) mechanically pressing and forming: adding the pug trapped in the step (2) into a forming die for forming, lightly beating for 3 times, then demolding, hanging and beating for 2 times, and then gradually increasing the pressure and beating again for 6 times, wherein the total beating times are 12 times, so as to obtain a semi-finished green brick;
(4) Baking and drying: and (3) drying the semi-finished green brick prepared in the step (3), and preserving the heat for 20 hours at the drying temperature of 210+/-10 ℃.
Comparative example 1
The ladle slag line brick of the comparative example comprises the following components in percentage by weight: 25 parts of 5-3mm 96.3 fused magnesia; 25 parts of 3-1mm 96.3 fused magnesia; 96.3 electric smelting magnesite 20 parts with the diameter of 1-0 mm; 17 parts of 200-mesh 96.3 fused magnesia fine powder; 8 parts of graphite; and (3) a composite binding agent: 0.1 part of ethylene glycol, 1.9 parts of phenolic resin and composite additive: 2.5 parts of Al-Mg alloy and 0.5 part of B 4 C.
Comparative example 2
The ladle slag line brick of the comparative example comprises the following components in percentage by weight: 24 parts of 5-3mm 96.3 fused magnesia; 3-1mm of 96.3 fused magnesia 27 parts; 19.5 parts of 1-0mm 96.3 electric smelting magnesia; 10 parts of 200-mesh 96.3 fused magnesia fine powder; 13.5 parts of graphite; and (3) a composite binding agent: 0 part of ethylene glycol, 3 parts of phenolic resin and a composite additive: 1 part of metallic aluminum and 2 parts of metallic silicon.
The preparation method of the ladle slag line brick in the comparative examples 1 and 2 comprises the following steps: aggregate, bonding agent, graphite, additive, discharging, forming, heat treatment and finished product, wherein the ladle slag line brick is obtained according to the mode, and the total mixing time is 30min.
The parameters for each of the above examples and comparative examples are shown in table 1:
The ladle bricks obtained in each example and comparative example were subjected to physical index and chemical index detection, and the detection results are shown in table 2 below:
Compared with comparative examples 1 and 2, the ladle slag line brick added with the reclaimed material has similar physical performance indexes with the same specification product without the reclaimed material, and the cost is lower under the same condition; example 1 has better bulk density, normal temperature compressive strength and apparent porosity compared with examples 2-4; thus, as can be seen from a comprehensive comparison, example 1 is a better choice in combination with the cost situation.
In addition, the inventors of the present invention conducted a great deal of experiments and analyses on the regenerated magnesium carbon material and the regenerated aluminum magnesium carbon material that have not been pretreated, and compared with the performance of the products obtained in examples 1 to 4, the regenerated magnesium carbon material and the regenerated aluminum magnesium carbon material that have not been pretreated, even if the mixed grinding technology in the prior art is adopted, can reduce most of the pseudo particles, but cannot remove most or all of them, and at the same time, cannot remove residual organic matters or organic compounds in some use processes, thereby preventing the regenerated magnesium carbon material and the regenerated aluminum magnesium carbon material from being regenerated.
The above description is further detailed description of the present invention in connection with the specific preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described above. And a person skilled in the art can make several simple deductions or substitutions without departing from the concept of the invention, which should be considered as falling within the protection scope of the invention.
Claims (10)
1. The slag line brick is characterized by comprising the following components in parts by weight: 5-0mm of regenerated magnesium carbon particles: 45-60 parts; 5-1mm of regenerated aluminum magnesium carbon particles: 10-15 parts of a lubricant; 96.3 electric smelting magnesia with the diameter of 1-0 mm: 5-15 parts; 200 mesh 96.3 electric smelting magnesite: 15-22 parts of a lubricant; graphite: 5-10 parts; a composite binder consisting of 0.1-0.2 parts of ethylene glycol and 1.9-3.8 parts of phenolic resin; a composite additive consisting of 2.5-5 parts of Al-Mg alloy and 0.5-1 part of B 4 C.
2. The slag line brick as set forth in claim 1, wherein the 5-0mm regenerated magnesium carbon particle size comprises a mixture of four of 5-3mm, 3-1mm, 1-0.5mm, 0.5-0mm, wherein the mass fraction of each particle size is:
3. the slag line brick as set forth in claim 2, wherein the 5-1mm secondary aluminum magnesium carbon particles have a particle size comprising a mixture of 5-3mm and 3-1mm, wherein the mass fraction of each particle size is:
5-10 parts of 5-3mm regenerated aluminum magnesium carbon material;
5-10 parts of 3-1mm regenerated aluminum magnesium carbon material.
4. The slag line brick according to claim 2, wherein the regenerated magnesium-carbon particles with the diameters of 5-3mm, 3-1mm, 1-0.5mm and 0.5-0mm are obtained by grinding and sieving.
5. The slag line brick according to claim 3, wherein the 5-3mm and 3-1mm regenerated aluminum-magnesium-carbon particles are obtained by mixing and grinding and then sieving.
6. The slag line brick as set forth in any one of claims 1 to 5 wherein the ratio of parts of ethylene glycol to phenolic resin is 1:19.
7. The slag line brick as set forth in any one of claims 1 to 5 wherein the ratio of parts of Al-Mg alloy to B 4 C is 5:1.
8. A method of making a slag line brick as claimed in any one of claims 1 to 7 comprising the steps of: the slag line brick is prepared from granular aggregate, 60wt% of binding agent, graphite, magnesia fine powder, 40wt% of binding agent, additive, discharging, forming, heat treatment and finished product.
9. The method for producing slag line brick according to claim 8, wherein after adding graphite, adding magnesia fine powder after premixing for 3 minutes, and the total mixing time is not less than 25 minutes.
10. Use of a slag line brick according to any one of claims 1-7 or a method of preparation according to any one of claims 8-9 for obtaining a slag line brick for use in a ladle.
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