CN112500134B - Magnesia carbon brick and preparation method thereof - Google Patents

Magnesia carbon brick and preparation method thereof Download PDF

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CN112500134B
CN112500134B CN202110160800.XA CN202110160800A CN112500134B CN 112500134 B CN112500134 B CN 112500134B CN 202110160800 A CN202110160800 A CN 202110160800A CN 112500134 B CN112500134 B CN 112500134B
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magnesia
equal
carbon brick
parts
granularity
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CN112500134A (en
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王伟伟
赵现堂
曹贺
刘丽
王志星
颜浩
任林
刘靖轩
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Beijing Lier High Temperature Materials Co Ltd
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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
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/402—Aluminium
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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
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    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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Abstract

The invention relates to the technical field of refractory materials, in particular to a magnesia carbon brick and a preparation method thereof; comprises 55-110 parts of fused magnesia, 12-16 parts of graphite, 1-3 parts of a bonding agent and 1-6 parts of an additive; wherein the binding agent is modified phenolic resin; the magnesia carbon brick is designed to solve the technical problem that the magnesia carbon brick in the prior art has poor high temperature resistance and is easy to oxidize due to the fact that phenolic resin is used as a bonding agent, so that the performance of the magnesia carbon brick is reduced.

Description

Magnesia carbon brick and preparation method thereof
Technical Field
The invention relates to the technical field of refractory materials, in particular to a magnesia carbon brick and a preparation method thereof.
Background
The magnesia carbon brick is a high-quality refractory material, has high refractoriness, good slag corrosion resistance, strong thermal shock resistance and small creep at high temperature, and has the advantages of the magnesia brick and the carbon brick, thereby being widely applied to the aspects of electric furnaces, converters, ladles and the like.
The magnesia carbon brick is composed of fused magnesia, graphite, a bonding agent, an additive and the like, and in the bonding agent, phenolic resin has the characteristics of good adhesion, corrosion resistance, thermal shock stability and high carbonization rate, so that the magnesia carbon brick is widely used as the bonding agent of the magnesia carbon brick. However, phenol resins have poor high temperature resistance and insufficient oxidation resistance. Along with the continuous improvement of the requirements on the steel, the smelting environment is severer, so that a high-temperature-resistant and oxidation-resistant magnesia carbon brick is urgently needed.
Therefore, in order to solve the above problems, the present invention is urgently needed to provide a magnesia carbon brick and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a magnesia carbon brick and a preparation method thereof, and the magnesia carbon brick is designed to solve the technical problem that the performance of the magnesia carbon brick is reduced due to poor high temperature resistance and easiness in oxidation of the magnesia carbon brick in the prior art which uses phenolic resin as a bonding agent.
The magnesia carbon brick provided by the invention comprises, by weight, 55-110 parts of fused magnesia, 12-16 parts of graphite, 1-3 parts of a bonding agent and 1-6 parts of an additive; wherein, the bonding agent is modified phenolic resin.
Preferably, the fused magnesite comprises 20-30 parts of fused magnesite with the granularity of 3-5mm and 20-40 parts of fused magnesite with the granularity of 1-3 mm; 10-20 parts of fused magnesia with the granularity of 0-1 mm; 5-20 parts of fused magnesia fine powder with the granularity of 0-0.088 mm.
Preferably, the solid content of the modified phenolic resin is more than or equal to 85 percent, the residual carbon of the modified phenolic resin is more than or equal to 52 percent, the free phenol is less than or equal to 10 percent, the water content is less than or equal to 3.0 percent, and the pH value is 6-7.
Preferably, the preparation method of the modified phenolic resin comprises the following steps:
preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2;
adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 deg.C, holding the temperature for 2-3 hr, adding acetic acid, and vacuum dehydrating to obtain modified phenolic resin.
Preferably, the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
preferably, MgO in the fused magnesia is more than or equal to 97.2, CaO is less than or equal to 2.0, and SiO is2≤1.5，Fe2O3Less than or equal to 0.8, and the volume density of the particles is more than or equal to 3.45 g/cm3。
Preferably, the granularity of the graphite is 0-0.088mm, wherein C in the graphite is more than or equal to 96.0%; the graphite is flake graphite.
Preferably, the additive is one or a mixture of more than two of aluminum powder, silicon powder and carbon-containing resin powder; wherein the grain size of the additive is less than or equal to 320 meshes.
Preferably, the MgO, the C and the bulk density of the obtained magnesia carbon brick are more than or equal to 76 percent and more than or equal to 12 percent respectively, and the bulk density is more than or equal to 3.10g/cm after being baked at 200 DEG C3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The invention also provides a magnesia carbon brick based on any one of the above, which comprises the following steps:
preparing modified phenolic resin;
weighing fused magnesia with the granularity of 3mm-5mm and fused magnesia with the granularity of 1mm-3mm according to the proportion, mixing for 1-2min, heating the modified phenolic resin to 40-50 ℃, mixing with the fused magnesia, and stirring for 2-3 min; adding fused magnesia with the granularity of 0-1mm and fused magnesia and graphite with the granularity of 0-0.088, stirring for 1-2min, adding an additive, and mixing for 5-25min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
Compared with the prior art, the magnesia carbon brick and the preparation method thereof provided by the invention have the following advantages:
1. according to the magnesia carbon brick provided by the invention, the magnesia carbon brick is prepared by taking the modified phenolic resin as the bonding agent, and the addition of the modified phenolic resin can avoid the reduction of the carbon residue value of the phenolic resin, can not cause the volume shrinkage of an adhesive layer, and can not cause the generation of air holes and cracks, so that the obtained magnesia carbon brick has the advantages of low compression strength, relatively high apparent porosity and relatively low volume density.
2. According to the magnesia carbon brick provided by the invention, the nano silicon carbide particles and the nano carbon black particles are added when the modified phenolic resin is synthesized, the specific surface area of the nano silicon carbide particles and the nano carbon black particles is large, the number of unpaired atoms on the surface is large, the surface activity is high, and after the nano silicon carbide particles and the nano carbon black particles are added, on one hand, the thermal stability of the phenolic resin can be improved, and the release amount and volume shrinkage of small molecules are reduced, so that the apparent porosity is reduced and the volume density is increased; on the other hand, after the nano silicon carbide particles and the nano carbon black particles are combined with the phenolic resin, when the brick is impacted, more micro cracks are generated, more impact energy is absorbed, and the impact strength is improved, so that the high-temperature strength and the oxidation resistance of the magnesia carbon brick are effectively improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The magnesia carbon brick provided by the invention comprises, by weight, 55-110 parts of fused magnesia, 12-16 parts of graphite, 1-3 parts of a bonding agent and 1-6 parts of an additive; wherein, the bonding agent is modified phenolic resin.
Specifically, the fused magnesite comprises 20-30 parts of fused magnesite with the granularity of 3-5mm and 20-40 parts of fused magnesite with the granularity of 1-3 mm; 10-20 parts of fused magnesia with the granularity of 0-1 mm; 5-20 parts of fused magnesia fine powder with the granularity of 0-0.088 mm.
Specifically, the solid content of the modified phenolic resin is more than or equal to 85 percent, the residual carbon of the modified phenolic resin is more than or equal to 52 percent, the free phenol is less than or equal to 10 percent, the water content is less than or equal to 3.0 percent, and the pH value is 6-7.
Specifically, the preparation method of the modified phenolic resin comprises the following steps:
preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2;
adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 deg.C, holding the temperature for 2-3 hr, adding acetic acid, and vacuum dehydrating to obtain modified phenolic resin.
Specifically, the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
specifically, MgO in the fused magnesia is more than or equal to 97.2, CaO is less than or equal to 2.0, and SiO is contained in the fused magnesia2≤1.5，Fe2O3Less than or equal to 0.8, and the volume density of the particles is more than or equal to 3.45 g/cm3。
Specifically, the granularity of the graphite is 0-0.088mm, wherein C in the graphite is more than or equal to 96.0%; the graphite is flake graphite.
Specifically, the additive is one or a mixture of more than two of aluminum powder, silicon powder and carbon-containing resin powder; wherein the grain size of the additive is less than or equal to 320 meshes.
Specifically, the MgO, C and bulk density of the obtained magnesia carbon brick are respectively more than or equal to 76 percent and more than or equal to 12 percent, and the bulk density after being baked at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The invention also provides a magnesia carbon brick based on any one of the above, which comprises the following steps:
s1) preparing modified phenolic resin;
s2), weighing fused magnesia with the granularity of 3mm-5mm and fused magnesia with the granularity of 1mm-3mm according to the proportion, mixing for 1-2min, heating the modified phenolic resin to 40-50 ℃, mixing with the fused magnesia, and stirring for 2-3 min; adding fused magnesia with the granularity of 0-1mm and fused magnesia and graphite with the granularity of 0-0.088, stirring for 1-2min, adding an additive, and mixing for 5-25min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
The magnesia carbon brick is prepared by taking the modified phenolic resin as the bonding agent, and by adding the modified phenolic resin, the reduction of the carbon residue value of the phenolic resin can be avoided, the volume shrinkage of an adhesive layer can not be caused, no air holes and cracks are generated, and the obtained magnesia carbon brick has low compression strength, relatively high apparent porosity and relatively low volume density.
According to the invention, when the modified phenolic resin is synthesized, the nano silicon carbide particles and the nano carbon black particles are added, so that the specific surface area of the nano silicon carbide particles and the specific surface area of the nano carbon black particles are large, the number of unpaired atoms on the surface is large, the surface activity is high, and after the nano silicon carbide particles and the nano carbon black particles are added, on one hand, the thermal stability of the phenolic resin can be improved, and the release amount and volume shrinkage of small molecules are reduced, so that the apparent porosity is reduced and the volume density is; on the other hand, after the nano silicon carbide particles and the nano carbon black particles are combined with the phenolic resin, when the brick is impacted, more micro cracks are generated, more impact energy is absorbed, and the impact strength is improved, so that the high-temperature strength and the oxidation resistance of the magnesia carbon brick are effectively improved.
Example one
Preparation of sample 1:
101) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
102) weighing 22 parts of fused magnesia with the granularity of 3mm-5mm and 24 parts of fused magnesia with the granularity of 1mm-3mm, mixing for 1-2min, mixing with 1 part of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 15 parts of fused magnesia with the granularity of 0-1mm, 20 parts of fused magnesia with the granularity of 0-0.088 and 16 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 4 parts of additive, mixing at high speed for 5-10min, and mixing at low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
MgO in fused magnesia is more than or equal to 97.2, CaO is less than or equal to 2.0, and SiO2≤1.5，Fe2O3Less than or equal to 0.8, and the volume density of the particles is more than or equal to 3.45 g/cm3(ii) a The granularity of the graphite is 0-0.088mm, wherein C in the graphite is more than or equal to 96.0%; the graphite is flaky graphite; wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1; the grain size of the additive is less than or equal to 320 meshes.
The physical and chemical indexes of the obtained sample 1 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The sample 1 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the prior art.
The sample 1 is used in a 65t converter in a certain steel mill, the average use frequency reaches 20000 furnaces, which is far higher than 17000 times of the average use frequency when the phenolic resin is used as a binding agent in the prior art.
Example two
Preparation of sample 2:
201) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
202) weighing 23 parts of fused magnesia with the granularity of 3-5mm and 26 parts of fused magnesia with the granularity of 1-3mm, mixing for 1-2min, mixing with 3 parts of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 18 parts of fused magnesia with the granularity of 0-1mm, 5 parts of fused magnesia with the granularity of 0-0.088 and 14 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 1 part of additive, mixing at high speed for 5-10min, and mixing at low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
MgO in fused magnesia is more than or equal to 97.2, CaO is less than or equal to 2.0, and SiO2≤1.5，Fe2O3Less than or equal to 0.8, and the volume density of the particles is more than or equal to 3.45 g/cm3(ii) a The granularity of the graphite is 0-0.088mm, wherein C in the graphite is more than or equal to 96.0%; the graphite is flaky graphite; wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1; the grain size of the additive is less than or equal to 320 meshes.
The physical and chemical indexes of the obtained sample 2 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa,the linear rate of change was 0-1.0%.
The sample 2 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the past.
The sample 2 is used in a 65t converter in a certain steel mill, the average use frequency reaches 20000 furnaces, which is far higher than 17000 times of the average use frequency when the phenolic resin is used as a binding agent in the prior art.
EXAMPLE III
Preparation of sample 3:
301) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
302) weighing 26 parts of fused magnesia with the granularity of 3mm-5mm and 35 parts of fused magnesia with the granularity of 1mm-3mm, mixing for 1-2min, mixing with 2 parts of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 16 parts of fused magnesia with the granularity of 0-1mm, 10 parts of fused magnesia with the granularity of 0-0.088 and 12 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 5 parts of an additive, mixing at a high speed for 5-10min, and mixing at a low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
Wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1.
The physical and chemical indexes of the obtained sample 1 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The sample 3 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the prior art.
Sample 3 was used in a 65t converter in a steel mill, and the average number of use was up to 20000, which is much higher than 17000 times of the average number of use in the case of using a conventional phenol resin as a binder.
Example four
Preparation of sample 4:
401) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
402) weighing 25 parts of fused magnesia with the granularity of 3-5mm and 30 parts of fused magnesia with the granularity of 1-3mm, mixing for 12min, mixing with 3 parts of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 18 parts of fused magnesia with the granularity of 0-1mm, 18 parts of fused magnesia with the granularity of 0-0.088 and 14 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 2 parts of an additive, mixing at a high speed for 5-10min, and mixing at a low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
Wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1.
The physical and chemical indexes of the obtained sample 1 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The sample 4 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the prior art.
Sample 4 was used in a 65t converter in a steel mill, and the average number of use was up to 20000, which is much higher than 17000 times of the average number of use in the case of using a conventional phenol resin as a binder.
EXAMPLE five
Preparation of sample 5:
501) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
502) weighing 30 parts of fused magnesia with the granularity of 3mm-5mm and 20 parts of fused magnesia with the granularity of 1mm-3mm, mixing for 12min, mixing with 3 parts of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 10 parts of fused magnesia with the granularity of 0-1mm, 10 parts of fused magnesia with the granularity of 0-0.088 and 15 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 3 parts of additive, mixing at high speed for 5-10min, and mixing at low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
Wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1.
The physical and chemical indexes of the obtained sample 1 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The sample 5 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the prior art.
Sample 5 was used in a 65t converter in a steel mill, and the average number of use was up to 20000, which is much higher than 17000 times of the average number of use in the case of using a conventional phenol resin as a binder.
EXAMPLE six
Preparation of sample 6:
601) preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2; adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin, wherein the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
602) weighing 20 parts of fused magnesia with the granularity of 3mm-5mm and 40 parts of fused magnesia with the granularity of 1mm-3mm, mixing for 12min, mixing with 3 parts of modified phenolic resin with the temperature of 40-50 ℃, and stirring for 2-3 min; adding 20 parts of fused magnesia with the granularity of 0-1mm, 15 parts of fused magnesia with the granularity of 0-0.088 and 15 parts of graphite with the granularity of 0-0.088, stirring for 1-2min, adding 6 parts of an additive, mixing at a high speed for 5-10min, and mixing at a low speed for 8-15min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
Wherein the additive is a mixture of aluminum powder, silicon powder and carbon-containing resin powder, and the aluminum powder: silicon powder: the mass ratio of the carbon-containing resin powder is 2:1: 1.
The physical and chemical indexes of the obtained sample 1 are as follows: MgO is more than or equal to 76 percent, C is more than or equal to 12 percent, and the bulk density after baking at 200 ℃ is more than or equal to 3.10g/cm3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
The sample 6 is used in a 100t ladle slag line area of a certain steel mill, the average use frequency reaches 45 furnaces, and is far higher than 25 times of the average use frequency when phenolic resin is used as a bonding agent in the prior art.
Sample 6 was used in a 65t converter in a steel mill, and the average number of use was up to 20000, which is much higher than 17000 times of the average number of use in the case of using a conventional phenol resin as a binder.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. A magnesia carbon brick is characterized in that: the graphite-graphite composite material comprises, by weight, 55-110 parts of fused magnesia, 12-16 parts of graphite, 1-3 parts of a bonding agent and 1-6 parts of an additive; wherein the binding agent is modified phenolic resin;
the preparation method of the modified phenolic resin comprises the following steps:
preparing a mixed solution of phenol and formaldehyde, wherein the molar ratio of the mixed solution of phenol and formaldehyde is 1:1.2;
adding nano silicon carbide and nano carbon black into the mixed solution of phenol and formaldehyde, wherein the total mass of the nano silicon carbide and the nano carbon black is 1 percent of that of the mixed solution of phenol and formaldehyde; adding sodium hydroxide, heating, stirring, heating to 80 ℃, keeping the temperature constant for 2-3 hours, adding acetic acid, and performing vacuum dehydration to obtain modified phenolic resin;
the mass ratio of the nano silicon carbide to the nano carbon black is 1:1.2;
the solid content of the modified phenolic resin is more than or equal to 85 percent, the residual carbon of the modified phenolic resin is more than or equal to 52 percent, the free phenol is less than or equal to 10 percent, the water content is less than or equal to 3.0 percent, and the pH value is 6-7.
2. The magnesia carbon brick of claim 1, wherein: the fused magnesia comprises 20-30 parts of fused magnesia with the granularity of 3-5mm and 20-40 parts of fused magnesia with the granularity of 1-3 mm; 10-20 parts of fused magnesia with the granularity of 0-1 mm; 5-20 parts of fused magnesia fine powder with the granularity of 0-0.088 mm.
3. The magnesia carbon brick of claim 1, wherein: in the fused magnesia, MgO is more than or equal to 97.2, CaO is less than or equal to 2.0, and SiO is2≤1.5，Fe2O3Less than or equal to 0.8, and the volume density of the particles is more than or equal to 3.45 g/cm3。
4. The magnesia carbon brick of claim 1, wherein: the granularity of the graphite is 0-0.088mm, wherein C in the graphite is more than or equal to 96.0%; the graphite is flake graphite.
5. The magnesia carbon brick of claim 1, wherein: the additive is one or a mixture of more than two of aluminum powder, silicon powder and carbon-containing resin powder; wherein the grain size of the additive is less than or equal to 320 meshes.
6. The magnesia carbon brick of claim 1, wherein: the obtained magnesia carbon brick has MgO content not less than 76%, C content not less than 12%, and bulk density not less than 3.10g/cm after baking at 200 deg.C3The apparent porosity is less than or equal to 5 percent, the compressive strength is more than or equal to 40MPa, and the linear change rate is 0-1.0 percent.
7. A magnesia carbon brick according to any one of claims 2 to 6, wherein: the method comprises the following steps:
preparing modified phenolic resin;
weighing fused magnesia with the granularity of 3mm-5mm and fused magnesia with the granularity of 1mm-3mm according to the proportion, mixing for 1-2min, heating the modified phenolic resin to 40-50 ℃, mixing with the fused magnesia, and stirring for 2-3 min; adding fused magnesia with the granularity of 0-1mm and fused magnesia and graphite with the granularity of 0-0.088, stirring for 1-2min, adding an additive, and mixing for 5-25min to obtain a magnesia carbon brick raw material;
controlling the temperature of the magnesia carbon brick raw material to be maintained at 40-60 ℃, pouring the magnesia carbon brick raw material into a mould, and carrying out heat treatment to obtain the magnesia carbon brick.
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JPH09132469A (en) * 1995-11-10 1997-05-20 Nippon Steel Corp Flame thermal spray material
CN101121590A (en) * 2007-07-10 2008-02-13 武汉理工大学 Steel slag coal ash self-cementing material
CN102161589A (en) * 2010-02-23 2011-08-24 宝山钢铁股份有限公司 Conductive magnesia-carbon brick for plasma gun
CN107673743A (en) * 2017-10-11 2018-02-09 马鞍山豹龙新型建材有限公司 A kind of production method of the low-carbon microdilatancy Ladle slag line magnesia carbon brick of slag corrosion resistance excellent ability
CN108083776A (en) * 2017-12-29 2018-05-29 江苏苏嘉集团新材料有限公司 A kind of magnesia carbon brick and preparation method thereof
CN108585806A (en) * 2018-06-15 2018-09-28 辽宁中镁控股股份有限公司 The method for manufacturing magnalium carbon refractory brick using regenerative magnesia-carbon brick and aluminium-magnesia carbon brick
CN109020572A (en) * 2018-08-27 2018-12-18 海城利尔麦格西塔材料有限公司 A kind of magnesia carbon brick with modified bonding agent preparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09132469A (en) * 1995-11-10 1997-05-20 Nippon Steel Corp Flame thermal spray material
CN101121590A (en) * 2007-07-10 2008-02-13 武汉理工大学 Steel slag coal ash self-cementing material
CN102161589A (en) * 2010-02-23 2011-08-24 宝山钢铁股份有限公司 Conductive magnesia-carbon brick for plasma gun
CN107673743A (en) * 2017-10-11 2018-02-09 马鞍山豹龙新型建材有限公司 A kind of production method of the low-carbon microdilatancy Ladle slag line magnesia carbon brick of slag corrosion resistance excellent ability
CN108083776A (en) * 2017-12-29 2018-05-29 江苏苏嘉集团新材料有限公司 A kind of magnesia carbon brick and preparation method thereof
CN108585806A (en) * 2018-06-15 2018-09-28 辽宁中镁控股股份有限公司 The method for manufacturing magnalium carbon refractory brick using regenerative magnesia-carbon brick and aluminium-magnesia carbon brick
CN109020572A (en) * 2018-08-27 2018-12-18 海城利尔麦格西塔材料有限公司 A kind of magnesia carbon brick with modified bonding agent preparation

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