CN106145971A - A kind of cracking resistance magnesia carbon brick and preparation method thereof - Google Patents
A kind of cracking resistance magnesia carbon brick and preparation method thereof Download PDFInfo
- Publication number
- CN106145971A CN106145971A CN201610530487.3A CN201610530487A CN106145971A CN 106145971 A CN106145971 A CN 106145971A CN 201610530487 A CN201610530487 A CN 201610530487A CN 106145971 A CN106145971 A CN 106145971A
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- China
- Prior art keywords
- magnesia
- carbon brick
- cracking resistance
- magnesia carbon
- parts
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011449 brick Substances 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 238000005336 cracking Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 21
- 239000008187 granular material Substances 0.000 claims abstract description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007767 bonding agent Substances 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 230000003026 anti-oxygenic effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical class [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000011339 hard pitch Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63472—Condensation polymers of aldehydes or ketones
- C04B35/63476—Phenol-formaldehyde condensation polymers
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of cracking resistance magnesia carbon brick, it is made up of the component of following weight portion: 75～80 parts of magnesia, 7～10 parts of basalt granules, 5～10 parts of copper sulphate pentahydrate, 0.3～0.5 part of hexamethylenetetramine, 15～18 parts of graphite, 3～5 parts of ceramic particle Al4SiC4, 3～5 parts of bonding agent.The cracking resistance magnesia carbon brick of the present invention can be prevented effectively from brick body slabbing, is substantially reduced carbon loss vector, improves resistance to slag and the antioxygenic property of magnesia carbon brick, improves service life, brick body quality and excellent performance.Present invention also offers a kind of cracking resistance magnesia carbon brick preparation method, processing step is simple, and workable, to equipment without particular/special requirement, preparation cost is low, is suitable for industrialized production.
Description
Technical field
The present invention relates to technical field of refractory materials, especially relate to a kind of cracking resistance magnesia carbon brick and preparation method thereof.
Background technology
Magnesia carbon brick is because having good thermal shock resistance and resistance to slag corrosion, so being widely used in ferrous metallurgical industry.
Causing product strength to reduce owing to carbon is oxidizable, corrosion resistance declines, and makes magnesia carbon brick lose the upper hand.For improving magnesia carbon brick at height
Oxidation resistance under the conditions of temperature, it is critical only that the decarbonization rate controlling material.A kind of the most conventional method is at magnesia carbon brick
The additive of the anti-oxidation of middle interpolation, common additive mainly has two classes, (1) metal or alloy fine powder；(2) nonmetal carefully
Powder.
Such as, application publication number CN101747065A, Shen Qing Publication day the Chinese patent of 2010.06.23 disclose one
Magnesia carbon brick, the raw material of this magnesia carbon brick is by 30-80 weight portion waste magnesia carbon bricks granule, 3-40 weight portion magnesia particle, 6-12 weight
Part graphite, 5-15 weight portion magnesia powder, 3-15 weight portion micro-powder as additive, 2.2-3.5 weight portion organic bond forms.This magnesium
Carbon brick adds micro-powder as additive (hard pitch powder, alumina powder, metallic aluminium powder, metallic silicon power, metal magnesium powder, boron nitride
In powder, carborundum powder any one or more than one) to improve magnesia carbon brick oxidation resistance at high temperature, its exist below
Not enough: (1) metal fine powder (such as metallic aluminium powder, metallic silicon power etc.) easily aoxidizes, already oxidised metal with in magnesia and graphite
Impurity easily there is disadvantageous reaction, the effect of flux can be played during oxidation, it is well known that in burned-magnesia brick, aluminium oxide is with high
The silicate mineral of calcium silicon ratio can react formation liquid phase, and refractoriness can produce significantly impact, gentle at molten steel, slag
Under the corrosion function of body, it is easy to cause goods to reduce service life；Additionally this magnesia carbon brick is in process of production, the metal of interpolation
Micropowder can cause magnesia carbon brick thermal expansion too high, thus produces the highest stress, causes magnesia carbon brick easily to ftracture；Rather than metal fine powder
The addition of (such as boron nitride powder, carborundum powder etc.) can affect again the resistance to slag of magnesia carbon brick；(2) in the preparation process of magnesia carbon brick,
It is easily generated slabbing, poor toughness.
Summary of the invention
The present invention is to solve the above-mentioned technical problem existing for the magnesia carbon brick of prior art, it is provided that a kind of formula closes
Natural sciences, can be prevented effectively from brick body slabbing, improve service life, the cracking resistance magnesia carbon brick of brick body quality and excellent performance.
Present invention also offers a kind of cracking resistance magnesia carbon brick preparation method, processing step is simple, workable, low cost,
It is suitable for industrialized production.
To achieve these goals, the present invention is by the following technical solutions:
A kind of cracking resistance magnesia carbon brick of the present invention, described cracking resistance magnesia carbon brick is made up of the component of following weight portion: 75～80 parts
Magnesia, 7～10 parts of basalt granules, 5～10 parts of copper sulphate pentahydrate, 0.3～0.5 part of hexamethylenetetramine, 15～18 parts of graphite,
3～5 parts of ceramic particle Al4SiC4, 3～5 parts of bonding agent.The present invention is directed to the defect existing for existing magnesia carbon brick formula, it is entered
Go re-optimization improvement, especially with the addition of basalt granule, copper sulphate pentahydrate and ceramic particle Al4SiC4, wherein basalt
Granule can make the crackle formed in brick body that skew and fork occur, and suppression long crack produces and changes direction, stops brick body simultaneously
The diffusion of internal fissure, from being effectively improved the thermal shock resistance of magnesia carbon brick, the combination water in copper sulphate pentahydrate loses under the high temperature conditions
After going, volume reduces so that produce short space around copper sulfate, and the thermal expansion of magnesia carbon brick can be effectively offset in this space, reduces
Internal stress, thus it is prevented effectively from magnesia carbon brick cracking, ceramic particle Al4SiC4Relative to conventional additives (such as metallic aluminium powder, metal
Silica flour etc.), it can reduce oxidized carbon, as free carbon, the carbon of self is joined supplementary carbon source in magnesia carbon brick, separately simultaneously
Outer Al4SiC4Decompose the Al generated2O3, SiC with MgO react and ultimately generate magnesium aluminate spinel and forsterite in brick body surface shape
Become protective layer to prevent from aoxidizing further, carbon loss vector can be substantially reduced, improve the resistance to slag of magnesia carbon brick, can be improved it and use the longevity
Life.
As preferably, described magnesia is mixed by the different-grain diameter magnesia of following weight portion: 20～25 part 3～5mm
Magnesia, 25～30 part 1～the magnesia of 2mm, 10～15 part 0.3～the magnesia of 0.5mm, 5～8 part 0.05～the magnesia of 0.08mm.
The particle size distribution of magnesia is the most crucial, and the specific surface area of the granule of small particle is relatively big, is adding the fashionable meeting more air of band people, is making
The generation probability of slabbing increases；And as the less slabbing that will also result in equally of large-size particles of framework material, the therefore present invention
By the strict particle size range controlling magnesia particle and addition, thus ensure to suppress closely knit product, effectively prevent slabbing
Generation.
As preferably, the particle diameter of described basalt granule is 20～25mm.The particle diameter of basalt granule is excessive, can increase on the contrary
Adding the crackle of brick body, particle diameter is too small, then effect is notable, therefore the present invention limits the particle diameter of basalt granule as 20～
25mm。
As preferably, described ceramic particle Al4SiC4Prepare by the following method: by aluminium powder, silica flour, carbon dust in molar ratio
After 4:1:4 mixing, add ethanol ball milling at least 24h in ball mill under nitrogen protection, in 1600 in vacuum sintering funace
～at 1800 DEG C, sinter 2～3h, grind after cooling, obtain ceramic particle Al4SiC4。
As preferably, described ceramic particle Al4SiC4Particle diameter be 5～10 μm.
As preferably, described bonding agent is phenol-formaldehyde resin modified, and described phenol-formaldehyde resin modified prepares by the following method:
(a) naphthalene sulphonate formaldehyde condensation polymer is dissolved in ethanol formed mass percent concentration be 0.5～1% mixing molten
Liquid.
B () is incorporated as mixed solution quality 1～the nano silicon of 1.5%, ultrasonic disperse, score in mixed solution
Dissipate liquid, stand-by.Easily reuniting after silicon dioxide dispersion, its dispersibility is always the technological difficulties of this area, the naphthalene in the present invention
Sodium sulfonate formaldehyde condensation products can be adsorbed on nanometer titanium dioxide silicon interface, makes nano silicon interface charged, and produces ζ electricity
Position, when scattered nano silicon is close to each other, separates due to the Coulomb repulsion of electric double layer, thus maintains its stably dispersing
Property so that it is being difficult to reunite, the present invention efficiently solves nano silicon by ultrasonic and naphthalenesulfonic acid-formaldehyde condensate and is difficult to
Scattered problem.
C () presses n (phenol): n (formaldehyde)=1:1.25～1.32, be dissolved in formalin by phenol, obtain premixed liquid.
D () presses v (dispersion liquid): v (premixed liquid)=1:5～6, add dispersion liquid while stirring, then press n in premixed liquid
(phenol): n (sodium hydroxide)=1:1.25～1.32, is added dropwise to sodium hydroxide solution while stirring, obtains reactant liquor.
D reactant liquor oil bath is heated by (), after heated and stirred to 50 DEG C, control heating rate be 0.5～0.6 DEG C/
Min, after being 90～95 DEG C to temperature, isothermal reaction 2～3h, it is 6.5～7.0 that acid adding is neutralized to pH, adds and produce after vacuum dehydration
Thing 0.5～the ethylene glycol of 1 times of volume, obtain phenol-formaldehyde resin modified.At present in magnesia carbon brick the most widely used phenolic resin as viscous
Mixture, but its heat decomposition temperature and oxidation resistance are poor, the most can not meet the use of novel refractory, the present invention
In with silicon dioxide, phenolic resin has been carried out modification, make the surface property of inorganic nano silicon dioxide and phenolic resin mutually
Join, improve the compatibility of the two, wettability and caking property, and effectively improve heat decomposition temperature and the antioxidation energy of phenolic resin
Power (heat decomposition temperature can improve about 190 DEG C, and oxidation of coal temperature can improve about 1200 DEG C), moreover it is possible to improve the strong of magnesia carbon brick
Degree, has widened its application.
A kind of cracking resistance magnesia carbon brick preparation method, concretely comprises the following steps: add in puddle mixer after being mixed by each raw material by proportioning
Row is mixing, mixing after add compressing adobe in punching block, finally to i.e. obtaining cracking resistance magnesia carbon brick after brick bat drying.
As preferably, mixing time is 40～50min, and briquetting pressure is 100～120Mpa, and baking temperature is 200～250
DEG C, drying time is 22～24h.
Therefore, there is advantages that
(1) the present invention is directed to the defect existing for existing magnesia carbon brick formula, it is carried out re-optimization improvement, especially
With the addition of basalt granule, copper sulphate pentahydrate and ceramic particle Al4SiC4, and the particle size distribution of magnesia is adjusted, can have
Effect avoids brick body slabbing, is substantially reduced carbon loss vector, improves resistance to slag and the antioxygenic property of magnesia carbon brick, improves the use longevity
Life, brick body quality and excellent performance；
(2) providing a kind of cracking resistance magnesia carbon brick preparation method, processing step is simple, workable, to equipment without special
Requirement, preparation cost is low, is suitable for industrialized production.
Detailed description of the invention
Below by detailed description of the invention, the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material are all commercially available or the industry is conventional, following
Method in embodiment, if no special instructions, is this area conventional method.
Embodiment 1
(1) ceramic particle Al is prepared4SiC4
After being mixed by aluminium powder, silica flour, carbon dust 4:1:4 in molar ratio, add ethanol ball milling in ball mill under nitrogen protection
At least 24h, sinters 3h in vacuum sintering funace at 1600 DEG C, grinds, obtain the ceramic particle that particle diameter is 5 μm after cooling
Al4SiC4, stand-by；
(2) phenol-formaldehyde resin modified is prepared
A naphthalene sulphonate formaldehyde condensation polymer is dissolved in ethanol formation mass percent concentration by () is the mixed solution of 0.5%；
B () is incorporated as the nano silicon of mixed solution quality 1%, ultrasonic disperse in mixed solution, obtain dispersion liquid,
Stand-by；
C () presses n (phenol): n (formaldehyde)=1:1.25, be dissolved in formalin by phenol, obtain premixed liquid；
D () presses v (dispersion liquid): v (premixed liquid)=1:5, add dispersion liquid while stirring, then press n (benzene in premixed liquid
Phenol): n (sodium hydroxide)=1:1.25, it is added dropwise to sodium hydroxide solution while stirring, obtains reactant liquor；
E reactant liquor oil bath is heated by (), after heated and stirred to 50 DEG C, controlling heating rate is 0.5 DEG C/min, extremely
After temperature is 90 DEG C, isothermal reaction 3h, it is 6.5 that acid adding is neutralized to pH, adds the second two of 0.5 times of volume of product after vacuum dehydration
Alcohol, obtains phenol-formaldehyde resin modified, stand-by；
(3) cracking resistance magnesia carbon brick is prepared
By 75kg magnesia, 7kg particle diameter is the basalt granule of 20mm, 5kg copper sulphate pentahydrate, 0.3kg hexamethylenetetramine,
15kg graphite, 3kg ceramic particle Al4SiC4, the weight proportion of 3kg bonding agent (phenol-formaldehyde resin modified) adds after being mixed by each raw material
Enter puddle mixer is carried out mixing, mixing after add compressing adobe in punching block, finally to i.e. obtaining cracking resistance magnesium after brick bat drying
Carbon brick, wherein magnesia is mixed by the different-grain diameter magnesia of following weight proportion: the magnesia of 20kg3mm, the magnesium of 25kg1mm
Sand, the magnesia of 10kg0.3mm, the magnesia of 5kg0.05mm, mixing time is 40min, and briquetting pressure is 100Mpa, baking temperature
Being 200 DEG C, drying time is 24h.
Embodiment 2
(1) ceramic particle Al is prepared4SiC4
After being mixed by aluminium powder, silica flour, carbon dust 4:1:4 in molar ratio, add ethanol ball milling in ball mill under nitrogen protection
At least 24h, sinters 2h in vacuum sintering funace at 1800 DEG C, grinds, obtain the ceramic particle that particle diameter is 10 μm after cooling
Al4SiC4, stand-by；
(2) phenol-formaldehyde resin modified is prepared
A naphthalene sulphonate formaldehyde condensation polymer is dissolved in ethanol formation mass percent concentration by () is the mixed solution of 1%；
B () is incorporated as the nano silicon of mixed solution quality 1.5%, ultrasonic disperse in mixed solution, obtain dispersion
Liquid, stand-by；
C () presses n (phenol): n (formaldehyde)=1:1.32, be dissolved in formalin by phenol, obtain premixed liquid；
D () presses v (dispersion liquid): v (premixed liquid)=1:6, add dispersion liquid while stirring, then press n (benzene in premixed liquid
Phenol): n (sodium hydroxide)=1:1.32, it is added dropwise to sodium hydroxide solution while stirring, obtains reactant liquor；
E reactant liquor oil bath is heated by (), after heated and stirred to 50 DEG C, controlling heating rate is 0.6 DEG C/min, extremely
After temperature is 95 DEG C, isothermal reaction 2h, it is 7.0 that acid adding is neutralized to pH, adds the ethylene glycol of 1 times of volume of product after vacuum dehydration,
Obtain phenol-formaldehyde resin modified, stand-by；
(3) cracking resistance magnesia carbon brick is prepared
By 80kg magnesia, 7kg particle diameter is the basalt granule of 25mm, 5kg copper sulphate pentahydrate, 0.5kg hexamethylenetetramine,
18kg graphite, 5kg ceramic particle Al4SiC4, the weight proportion of 5kg bonding agent (phenol-formaldehyde resin modified) adds after being mixed by each raw material
Enter puddle mixer is carried out mixing, mixing after add compressing adobe in punching block, finally to i.e. obtaining cracking resistance magnesium after brick bat drying
Carbon brick, wherein magnesia is mixed by the different-grain diameter magnesia of following weight proportion: the magnesia of 25kg5mm, the magnesium of 30kg2mm
Sand, the magnesia of 15kg0.5mm, the magnesia of 8kg0.08mm, mixing time is 50min, and briquetting pressure is 120Mpa, baking temperature
Being 250 DEG C, drying time is 22h.
Embodiment 3
(1) ceramic particle Al is prepared4SiC4
After being mixed by aluminium powder, silica flour, carbon dust 4:1:4 in molar ratio, add ethanol ball milling in ball mill under nitrogen protection
At least 24h, sinters 2.5h in vacuum sintering funace at 1700 DEG C, grinds, obtain the ceramic particle that particle diameter is 8 μm after cooling
Al4SiC4, stand-by；
(2) phenol-formaldehyde resin modified is prepared
A naphthalene sulphonate formaldehyde condensation polymer is dissolved in ethanol formation mass percent concentration by () is the mixed solution of 0.7%；
B () is incorporated as the nano silicon of mixed solution quality 1.2%, ultrasonic disperse in mixed solution, obtain dispersion
Liquid, stand-by；
C () presses n (phenol): n (formaldehyde)=1:1.28, be dissolved in formalin by phenol, obtain premixed liquid；
D () presses v (dispersion liquid): v (premixed liquid)=1:5.5, add dispersion liquid while stirring, then press n (benzene in premixed liquid
Phenol): n (sodium hydroxide)=1:1.26, it is added dropwise to sodium hydroxide solution while stirring, obtains reactant liquor；
E reactant liquor oil bath is heated by (), after heated and stirred to 50 DEG C, controlling heating rate is 0.55 DEG C/min,
After being 92 DEG C to temperature, isothermal reaction 2.5h, it is 6.8 that acid adding is neutralized to pH, adds the second of 0.7 times of volume of product after vacuum dehydration
Glycol, obtains phenol-formaldehyde resin modified, stand-by；
(3) cracking resistance magnesia carbon brick is prepared
By 78kg magnesia, 8kg particle diameter is the basalt granule of 22mm, 7kg copper sulphate pentahydrate, 0.4kg hexamethylenetetramine,
17kg graphite, 4kg ceramic particle Al4SiC4, after each raw material is mixed by the weight of 4kg bonding agent (phenol-formaldehyde resin modified)
Add in puddle mixer carry out mixing, mixing after add compressing adobe in punching block, finally to i.e. obtaining cracking resistance after brick bat drying
Magnesia carbon brick, wherein magnesia is mixed by the different-grain diameter magnesia of following Different Weight part: the magnesia of 22kg4mm, 28kg1.5mm
Magnesia, the magnesia of 12kg0.4mm, the magnesia of 6kg0.07mm, mixing time is 45min, and briquetting pressure is 110Mpa, be dried
Temperature is 230 DEG C, and drying time is 22.5h.
The cracking resistance magnesia carbon brick performance indications of the present invention are as follows:
The porosity (%): 2.1；
Bulk density (g/cm3): 3.02；
Decarburized layer (mm): 1.32；
Compressive resistance (Mpa): 46；
High temperature break resistant intensity (Mpa, 1400 DEG C × 1h bury carbon): 20.2.
Embodiment described above is the one preferably scheme of the present invention, not makees the present invention any pro forma
Limit, on the premise of without departing from the technical scheme described in claim, also have other variant and remodeling.
Claims (8)
1. a cracking resistance magnesia carbon brick, it is characterised in that described cracking resistance magnesia carbon brick is made up of the component of following weight portion: 75～80 parts
Magnesia, 7～10 parts of basalt granules, 5～10 parts of copper sulphate pentahydrate, 0.3～0.5 part of hexamethylenetetramine, 15～18 parts of graphite,
3～5 parts of ceramic particle Al4SiC4, 3～5 parts of bonding agent.
A kind of cracking resistance magnesia carbon brick the most according to claim 1, it is characterised in that described magnesia is by the difference of following weight portion
Particle diameter magnesia mixes: 20～25 part 3～the magnesia of 5mm, 25～30 part 1～the magnesia of 2mm, 10～15 part 0.3～0.5mm
Magnesia, 5～8 part 0.05～the magnesia of 0.08mm.
A kind of cracking resistance magnesia carbon brick the most according to claim 1, it is characterised in that the particle diameter of described basalt granule be 20～
25mm。
A kind of cracking resistance magnesia carbon brick the most according to claim 1, it is characterised in that described ceramic particle Al4SiC4By following
Method prepares: after being mixed by aluminium powder, silica flour, carbon dust 4:1:4 in molar ratio, add ethanol ball milling in ball mill under nitrogen protection
At least 24h, sinters 2～3h in vacuum sintering funace at 1600～1800 DEG C, grinds, obtain ceramic particle after cooling
Al4SiC4。
A kind of cracking resistance magnesia carbon brick the most according to claim 4, it is characterised in that described ceramic particle Al4SiC4Particle diameter be
5～10 μm.
A kind of cracking resistance magnesia carbon brick the most according to claim 1, it is characterised in that described bonding agent is phenol-formaldehyde resin modified,
Described phenol-formaldehyde resin modified prepares by the following method:
A naphthalene sulphonate formaldehyde condensation polymer is dissolved in ethanol and forms the mixed solution that mass percent concentration is 0.5～1% by ()；
B () is incorporated as mixed solution quality 1～the nano silicon of 1.5%, ultrasonic disperse in mixed solution, obtain dispersion
Liquid, stand-by；
C () presses n (phenol): n (formaldehyde)=1:1.25～1.32, be dissolved in formalin by phenol, obtain premixed liquid；
D () presses v (dispersion liquid): v (premixed liquid)=1:5～6, add dispersion liquid while stirring, then press n (benzene in premixed liquid
Phenol): n (sodium hydroxide)=1:1.25～1.32, it is added dropwise to sodium hydroxide solution while stirring, obtains reactant liquor；
E reactant liquor oil bath is heated by (), after heated and stirred to 50 DEG C, controlling heating rate is 0.5～0.6 DEG C/min,
After being 90～95 DEG C to temperature, isothermal reaction 2～3h, it is 6.5～7.0 that acid adding is neutralized to pH, adds product 0.5 after vacuum dehydration
～the ethylene glycol of 1 times of volume, obtain phenol-formaldehyde resin modified.
7. a cracking resistance magnesia carbon brick preparation method as claimed in claim 1, it is characterised in that concretely comprise the following steps: will by proportioning
Add in puddle mixer after the mixing of each raw material carry out mixing, mixing after add compressing adobe in punching block, finally adobe is done
Cracking resistance magnesia carbon brick is i.e. obtained after dry.
Cracking resistance magnesia carbon brick preparation method the most according to claim 7, it is characterised in that mixing time is 40～50min, becomes
Type pressure is 100～120Mpa, and baking temperature is 200～250 DEG C, and drying time is 22～24h.
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| CN108585895A (en) * | 2018-05-10 | 2018-09-28 | 苏州佳耐材料科技有限公司 | A method of addition ternary compound prepares high-performance magnesia carbon brick |
| CN109942198A (en) * | 2019-05-05 | 2019-06-28 | 商洛学院 | The method for using hot pressing sintering method to prepare glass water-permeable brick as raw material using Pb-Zn tailings |
| CN111533538A (en) * | 2020-04-11 | 2020-08-14 | 北京利尔高温材料股份有限公司 | Furnace lining material and application method thereof |
| CN116715530A (en) * | 2023-06-02 | 2023-09-08 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of spinel carbon material with low thermal expansion rate |
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| CN105503212A (en) * | 2015-12-21 | 2016-04-20 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick and preparation method thereof |
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| CN107540394A (en) * | 2017-08-25 | 2018-01-05 | 上海利尔耐火材料有限公司 | A kind of dry materials, and its preparation method and application |
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