CN113248269B - Magnesia carbon brick added with composite binder and preparation method thereof - Google Patents
Magnesia carbon brick added with composite binder and preparation method thereof Download PDFInfo
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- CN113248269B CN113248269B CN202110535296.7A CN202110535296A CN113248269B CN 113248269 B CN113248269 B CN 113248269B CN 202110535296 A CN202110535296 A CN 202110535296A CN 113248269 B CN113248269 B CN 113248269B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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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
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a magnesia carbon brick added with a composite bonding agent and a preparation method thereof, relating to the technical field of magnesia carbon bricks, wherein the ingredients comprise magnesia, a carbon source, a bonding agent and an antioxidant, and the content ratio of the magnesia to the carbon source to the bonding agent to the antioxidant is 1.5: 0.1. the novel binding agent prepared from thermosetting phenolic resin, composite binding agent (nano carbon black, phenolic resin and asphalt modified phenolic resin) and Carbores P-type phenolic oil binding agent ensures carbon source on one hand and improves thermal shock stability and high temperature strength of the magnesia carbon brick on the other hand, and the novel binding agent is prepared from TiO 2 -Al, alumina micropowder and B 4 The antioxidant consisting of the C-C composite powder not only enhances the strength and the hardness of the magnesia carbon brick, but also ensures that the magnesia carbon brick has excellent oxidation resistance, and simultaneously can supplement a carbon source and improve the thermal shock resistance of the magnesia carbon brick.
Description
Technical Field
The invention relates to the technical field of magnesia carbon bricks, in particular to a magnesia carbon brick added with a composite binder and a preparation method thereof.
Background
The magnesia carbon brick is a novel building stacking material, the raw materials of the magnesia carbon brick are magnesia, a carbon source, a bonding agent and an antioxidant, the building material is continuously reformed along with the continuous development of modern science and technology, and the raw material composition in the magnesia carbon brick is correspondingly changed, so that the magnesia carbon brick with better quality and more excellent performance is obtained.
The bonding agent of the magnesia carbon brick is selected to be a composite bonding agent at present, the composite bonding agent can make up the performance defect of the previous magnesia carbon brick, and the performance improvement of the magnesia carbon brick has obvious effect.
The existing magnesia carbon brick has limited carbon source selection, few carbon source materials meeting the requirements are available in consideration of factors such as current cost, environmental protection and the like, and the addition of a general bonding agent can not generate a recarburization effect of 1+1 & gt 2, so that an improvement method for saving cost, ensuring carbon content and ensuring comprehensive performance of the magnesia carbon brick needs to be quickly found out
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a magnesia carbon brick added with a composite binder and a preparation method thereof, and solves the problems in the background art.
In order to achieve the purpose, the invention is realized by the following technical scheme: the magnesia carbon brick added with the composite bonding agent comprises magnesite, a carbon source, a bonding agent and an antioxidant, wherein the content ratio of the magnesite to the carbon source to the bonding agent to the antioxidant is 1.5: 0.1.
optionally, the magnesite is fused magnesite, magnesium oxide and asphalt, wherein the fused magnesite is calculated according to the content ratio: magnesium oxide: pitch = 2.
Optionally, the fused magnesite and the magnesium oxide are ground into powder and sieved by a 80-mesh sieve.
Optionally, the carbon source specifically selects flake graphite, carbon black N220 and special graphite, wherein the content ratio of flake graphite: carbon black N220: special graphite = 4.
Optionally, the binder is specifically a thermosetting phenolic resin, a composite binder, and a Carbores P-type phenol oil binder, wherein the thermosetting phenolic resin, the nano carbon black, the phenolic resin, and the Carbores P-type phenol oil binder have equal contents.
Optionally, the composite binder is prepared by mixing nano carbon black, phenolic resin and asphalt modified phenolic resin in equal proportion.
Optionally, the antioxidant is specifically made of TiO 2 -Al, alumina micropowder and
C-C composite powder, tiO in percentage by content 2 -Al: alumina micropowder:
C-C composite powder = 1.
Based on the raw materials, the invention also discloses a preparation method of the magnesia carbon brick added with the composite binder.
Optionally, the preparation method specifically comprises the following steps:
(1) preparing a binding agent:
a. adding nano carbon black, phenolic resin and asphalt modified phenolic resin in equal ratio into a container, and stirring and mixing at a high speed to obtain a composite binder;
b. sequentially adding thermosetting phenolic resin and Carbores P-type phenolic oil binder into the composite binder, and fully stirring and mixing to obtain the binder;
(2) preparing magnesia: taking asphalt as a dispersion medium, adding fused magnesia and magnesia, and uniformly stirring and mixing to obtain magnesia;
(3) adding magnesia into the bonding agent, and fully stirring and mixing;
(4) uniformly mixing the flake graphite, the carbon black N220 and the special graphite in advance, adding the uniformly mixed carbon source into a binding agent, and fully stirring and mixing;
(5) mixing TiO with 2 Al, alumina micropowder and
sequentially adding the C-C composite powder into the mixture, and fully stirring to ensure that the final mixture is uniform in texture;
(6) and (5) molding the brick, putting the brick into a furnace, and sintering the brick.
The invention provides a magnesia carbon brick added with a composite bonding agent and a preparation method thereof, and the magnesia carbon brick has the following beneficial effects:
1. according to the magnesia carbon brick added with the composite bonding agent and the preparation method thereof, the content of magnesia in the magnesia carbon brick is ensured by electric melting magnesia, the chemical corrosion resistance of the magnesia carbon brick can be effectively improved by adding magnesia, the problem of poor thermal spalling of the magnesia carbon brick can be solved by asphalt, and the thermal expansion of magnesia particles in the use process can be reduced by preparing a thin asphalt coating on the surface of the magnesia particles, so that the thermal shock stability of the magnesia carbon brick can be improved.
2. According to the magnesia carbon brick added with the composite binder and the preparation method thereof, the carbon black N220 and the special graphite are added, so that the performance of the magnesia carbon brick can be effectively improved, the addition of the carbon black N220 enables the magnesia carbon brick to have more excellent thermal shock stability, the addition of the carbon black N220 is less, the cost consumption is low, the achieved performance is better than that of a graphite carbon source with normal dosage, and the thermal shock stability of the magnesia carbon brick can be obviously improved by the added special graphite and crystalline flake graphite mixed carbon source.
3. According to the magnesia carbon brick added with the composite binding agent and the preparation method thereof, the Carbores P-type phenolic oil binding agent is used for effectively improving the physical property and the chemical property of the magnesia carbon brick, the Carbores P-type phenolic oil binding agent is adopted and can be used as the binding agent on the one hand and also can be used as one of carbon sources on the other hand, and meanwhile, the nano carbon black is combined with phenolic resin, so that the graphitization degree of the binding agent after carbonization is improved, micropores are formed in a matrix, the mechanical properties of the magnesia carbon brick, such as normal-temperature breaking strength, high-temperature breaking strength and the like, are improved, the graphitizable asphalt modified phenolic resin is introduced into the phenolic resin, the magnesia carbon brick can be carbonized into secondary carbon with a flowing or mosaic structure under the using environment of the magnesia carbon brick, or nano carbon fiber is formed in situ, the carbon structure of the traditional binding agent is improved, and meanwhile, the nano carbon fiber has the reinforcing effect, so that the thermal shock stability and the high-temperature strength of the magnesia carbon brick can be better improved.
4. The magnesia carbon brick added with the composite binder and the preparation method thereof are added with TiO 2 After Al, tiCN and TiC crystal phases are generated in the magnesia carbon brick, so that the magnesia carbon brick has excellent mechanical, thermal and chemical properties, and the alumina micro powder and the magnesia can produce the magnesia-alumina spinel which is continuously distributed in situ at high temperature, thereby enhancing the ceramic bonding of the magnesia carbon brick,
the C-C composite powder can be used as a carbon source and an antioxidant in a low-carbon magnesia carbon brick, so that the oxidation resistance of the magnesia carbon brick is obviously superior to that of the magnesia carbon brick which takes graphite or carbon black as the carbon source and uses industry
C is antioxidant low-carbon magnesia carbon brick, and simultaneously
The introduction of the C-C composite powder can effectively improve the heat resistance of the magnesia carbon brickShock property.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
The magnesia carbon brick added with the composite bonding agent comprises magnesite, a carbon source, a bonding agent and an antioxidant, wherein the content ratio of the magnesite to the carbon source to the bonding agent to the antioxidant is 1.5: 0.1;
the magnesite is specifically selected from fused magnesite, magnesium oxide and asphalt, wherein the fused magnesite comprises the following components in percentage by content: magnesium oxide: pitch = 2;
further, grinding the fused magnesia and the magnesium oxide into powder, and sieving the powder by a 80-mesh sieve;
the content of magnesia in the magnesia carbon brick is ensured by electric melting magnesia, the chemical corrosion resistance of the magnesia carbon brick can be effectively improved by adding magnesia, the problem of poor thermal spalling property of the magnesia carbon brick can be solved by asphalt, and the thermal expansion of magnesia particles in the using process can be reduced by preparing a thin asphalt coating on the surface of the magnesia particles, so that the thermal shock stability of the magnesia carbon brick can be improved;
the carbon source specifically selects crystalline flake graphite, carbon black N220 and special graphite, wherein the crystalline flake graphite comprises the following components in percentage by content: carbon black N220: special graphite = 4;
the addition of the carbon black N220 and the special graphite can effectively improve the performance of the magnesia carbon brick, the addition of the carbon black N220 enables the magnesia carbon brick to have more excellent thermal shock stability, the addition amount of the carbon black N220 is less, the cost consumption is low, the achieved performance is better than that of a graphite carbon source with normal consumption, and the thermal shock stability of the magnesia carbon brick can be obviously improved by the added special graphite and flake graphite mixed carbon source;
the binding agent is specifically thermosetting phenolic resin, composite binding agent and Carbores P-type phenolic oil binding agent, wherein the thermosetting phenolic resin, the nano carbon black, the phenolic resin and the Carbores P-type phenolic oil binding agent have equal content;
the Carbores P-type phenol oil binder has low content of benzopyrene, forms an anisotropic structure similar to graphite after carbonization, can effectively improve the physical property and the chemical property of the magnesia carbon brick by using the Carbores P-type phenol oil binder, and can be used as a binder and one of carbon sources on the one hand;
the composite binder is prepared by mixing nano carbon black, phenolic resin and asphalt modified phenolic resin in equal ratio;
the nano carbon black is combined with the phenolic resin, so that the graphitization degree of the binding agent after carbonization is improved, micro pores are formed in a matrix, and the mechanical properties of the magnesia carbon brick, such as normal-temperature breaking strength, high-temperature breaking strength and the like, are improved, a graphitizable carbon precursor, namely asphalt modified phenolic resin, is introduced into the phenolic resin to generate a composite binding agent with high carbon residue rate and good high-temperature property, and the binding agent can be carbonized into secondary carbon with a flowing or mosaic structure under the using environment of the magnesia carbon brick, or form nano carbon fiber in situ, so that the carbon structure of the traditional binding agent is improved, and meanwhile, the nano carbon fiber has a reinforcing effect, so that the thermal shock stability and the high-temperature strength of the magnesia carbon brick can be better improved;
the antioxidant is specifically made of TiO 2 Al, alumina micropowder and
C-C composite powder, tiO in percentage by content 2 -Al: aluminum oxide micro powder:
C-C composite powder = 1;
addition of TiO 2 After Al, tiCN and TiC crystal phases are generated in the magnesia carbon brick, so that the magnesia carbon brick has excellent mechanical, thermal and chemical properties, and the alumina micro powder and the magnesia can produce the magnesia-alumina spinel which is continuously distributed in situ at high temperature, thereby enhancing the ceramic bonding of the magnesia carbon brick,
C-C composite powderCan be used as a carbon source and an antioxidant in a low-carbon magnesia carbon brick, so that the oxidation resistance of the magnesia carbon brick is obviously superior to that of the magnesia carbon brick which takes graphite or carbon black as the carbon source and takes industrial carbon black as the carbon source
C is antioxidant low-carbon magnesia carbon brick, and simultaneously
The introduction of the C-C composite powder can effectively improve the thermal shock resistance of the magnesia carbon brick.
Example 2
A preparation method of a magnesia carbon brick added with a composite binder comprises the following specific steps:
(1) preparing a binding agent:
a. adding nano carbon black, phenolic resin and asphalt modified phenolic resin in equal ratio into a container, and stirring and mixing at a high speed to obtain a composite binding agent;
b. sequentially adding thermosetting phenolic resin and Carbores P-type phenolic oil binder into the composite binder, and fully stirring and mixing to obtain the binder;
(2) preparing magnesia: adding fused magnesia and magnesia into asphalt as a dispersion medium, and uniformly stirring and mixing to obtain magnesia;
(3) adding magnesia into the bonding agent, and fully stirring and mixing;
(4) uniformly mixing the flake graphite, the carbon black N220 and the special graphite in advance, adding the uniformly mixed carbon source into a binding agent, and fully stirring and mixing;
(5) mixing TiO with 2 Al, alumina micropowder and
sequentially adding the C-C composite powder into the mixture, and fully stirring to ensure that the final mixture is uniform in texture;
(6) and (5) feeding the bricks into a furnace, and sintering the bricks.
In conclusion, the magnesia carbon brick added with the composite bonding agent and the preparation method thereof adopt a low-carbon design, reduce the use of carbon source, and reduce the consumption of carbon source in the bonding agentAnd the selection of the antioxidant, the secondary addition of a carbon source is emphasized to ensure that the carbon content in the magnesia carbon brick is sufficient, and the novel binding agent prepared from thermosetting phenolic resin, composite binding agent (nano carbon black, phenolic resin and asphalt modified phenolic resin) and Carbores P-type phenolic oil binding agent ensures the carbon source on one hand and also improves the thermal shock stability and high-temperature strength of the magnesia carbon brick on the other hand, and TiO is used for improving the thermal shock stability and the high-temperature strength of the magnesia carbon brick 2 Al, alumina micropowder and
the antioxidant consisting of the C-C composite powder not only enhances the strength and the hardness of the magnesia carbon brick, but also ensures that the magnesia carbon brick has excellent oxidation resistance, and simultaneously can supplement a carbon source and improve the thermal shock resistance of the magnesia carbon brick.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. A magnesia carbon brick added with composite binder is characterized in that: the magnesia carbon brick comprises magnesite, a carbon source, a bonding agent and an antioxidant, wherein the content ratio of the magnesite to the carbon source to the bonding agent to the antioxidant is 1.5;
the magnesite is specifically selected from fused magnesite, magnesia and asphalt, wherein the fused magnesite comprises the following components in percentage by weight, magnesia and asphalt = 1;
the carbon source specifically selects crystalline flake graphite, carbon black N220 and special graphite, wherein the ratio of the crystalline flake graphite to the carbon black N220 to the special graphite = 4;
the binding agent is specifically thermosetting phenolic resin, a composite binding agent and a carbores P type phenolic oil binding agent, wherein the thermosetting phenolic resin, the nano carbon black, the phenolic resin and the carbores P type phenolic oil binding agent have equal contents;
the composite binder is prepared by mixing nano carbon black, phenolic resin and asphalt modified phenolic resin in equal proportion;
the antioxidant is specifically made of TiO 2 -Al, alumina micropowder and B 4 C-C composite powder, tiO in percentage by content 2 Al fine alumina powder B 4 C-C composite powder = 1;
wherein TiCN and TiC crystal phases are generated in the magnesia carbon brick.
2. The magnesia carbon brick added with composite binder according to claim 1, wherein: the fused magnesite and the magnesium oxide are ground into powder and sieved by a 80-mesh sieve.
3. A preparation method of a magnesia carbon brick added with a composite binder is characterized by comprising the following steps: the preparation method comprises the magnesia carbon brick added with the composite binder according to any one of claims 1 or 2, and comprises the following specific steps:
(1) preparing a binding agent:
a. adding nano carbon black, phenolic resin and asphalt modified phenolic resin in equal ratio into a container, and stirring and mixing at a high speed to obtain a composite binding agent;
b. sequentially adding thermosetting phenolic resin and carbores P type phenolic oil binder into the composite binder, and fully stirring and mixing to obtain the binder;
(2) preparing magnesia: adding fused magnesia and magnesia into asphalt as a dispersion medium, and uniformly stirring and mixing to obtain magnesia;
(3) adding magnesia into the bonding agent, and fully stirring and mixing;
(4) uniformly mixing the flake graphite, the carbon black N220 and the special graphite in advance, adding the uniformly mixed carbon source into a binding agent, and fully stirring and mixing;
(5) adding TiO into the mixture 2 -Al, alumina micropowder and B 4 Sequentially adding the C-C composite powder into the mixture, and fully stirring to ensure that the final mixture is uniform in texture;
(6) and (5) molding the brick, putting the brick into a furnace, and sintering the brick.
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