CN108484130A - A kind of low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing - Google Patents

A kind of low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing Download PDF

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Publication number
CN108484130A
CN108484130A CN201810613284.XA CN201810613284A CN108484130A CN 108484130 A CN108484130 A CN 108484130A CN 201810613284 A CN201810613284 A CN 201810613284A CN 108484130 A CN108484130 A CN 108484130A
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carbon
magnesia
nano
brick
enhancing
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马北越
任鑫明
苏畅
张亚然
于敬雨
石明东
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Yingkou Shi Yuan Refractory Co Ltd
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Yingkou Shi Yuan Refractory 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
    • C04B35/043—Refractories from grain sized mixtures
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/424—Carbon black
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention belongs to technical field of refractory materials, and in particular to a kind of low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing.Nanometer carbon content is 2 4% in the low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present invention, is the 50% of current mainstream magnesia carbon brick carbon content.The sintering character of the magnesia carbon brick, antioxygenic property, thermal shock performance do not reduce, even better than existing magnesia carbon brick.Total carbon needed for the present invention reduces half, not only saves cost of material, but also extend the service life of magnesia carbon brick；In addition, manufacturing cost of the present invention is low, and it is simple for process, it is suitable for industrial applications and a wide range of popularization.

Description

A kind of low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing
Technical field
The invention belongs to technical field of refractory materials, and in particular to a kind of low carbon magnesia carbon brick of nano-sized carbon enhancing and its preparation Method.
Background technology
Magnesia carbon brick (MgO-C) refractory material is widely used in steel and the neck such as coloured by its own excellent slag resistance Domain.There are carbon in magnesia carbon brick refractory material many positive effects, content to be generally 12~18% (w).On the one hand, carbon has Higher fusing point (3823K) and lower angle of wetting (to clinker), therefore the corrosion resistance of refractory material can be promoted；Another party Face, since carbon has low thermal expansion, high-termal conductivity and low elastic modulus so that the thermal shock resistance of refractory material is also changed It is kind.
But with the raising of the development of smelting technique and product performance demands, it has been found that, higher carbon contains in magnesia carbon brick Amount also brings along some disadvantages, the inherent defect easily aoxidized such as carbon electrode.To solve this defect, people are usually using anti-oxidant Agent delays the oxidation of carbon, but this can introduce new impurity again, influence the performance of final products.Meanwhile carbon content increases certainty Refractory material thermal conductivity can be made to increase, so as to cause higher energy consumption.Therefore, the exploitation of low carbon magnesia carbon brick refractory material become to It closes important.
Invention content
In view of the problems of the existing technology, the present invention provides the low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing, Purpose is 50% nano-sized carbon less than current mainstream magnesia carbon brick carbon content by introducing, solves existing magnesia carbon brick carbon content mistake The problems such as height or insufficient low carbon magnesia carbon brick performance, and the sintering character of the magnesia carbon brick, antioxygenic property, thermal shock performance do not drop It is low, even better than existing magnesia carbon brick.
The low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present invention, according to mass percent, raw material magnesia 90%~95%, nanometer Carbon 2~4%, antioxidant 2%~3%, bonding agent 4%.
The preparation method of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present invention follows the steps below：
(1) dispensing：In mass ratio, magnesia 90%~95%, nano-sized carbon 2~4%, antioxidant 2%~3%, bonding agent 4% carries out dispensing；
(2) it is kneaded：By above-mentioned dispensing according to certain sequence the mixing in batch mixer；
(3) it suppresses：By the forcing press compression moulding of the powder of mixing；
(4) dry：The magnesia carbon brick green compact pressed are dried in drying box to get finished product.
Wherein, the magnesia is fused magnesite, wherein MgO mass accounting >=97%, CaO/SiO2Mass ratio >=2, grain Degree≤10mm.
Carbonaceous amount accounting >=98% in the nano-sized carbon, be nano oxidized graphite flake, carbon nanotube, carbon black, activated carbon, Coke or in which two kinds of arbitrary ratio mixing.
The antioxidant is Ca, Si, Al, SiC, Si3N4One of which, granularity≤200 μm.
The bonding agent is one kind of phenolic resin, synthetic resin, magnalium cementing agent.
Batch mixing sequence is：Magnesia, nano-sized carbon, antioxidant, bonding agent and the magnesia powder of big granularity and middle granularity, Mixing time is using 5min~10min as interval.
Pressure when the described compression moulding is 100MPa~300MPa.
The drying temperature is 100 DEG C~300 DEG C.
The heat treatment time is 8h~12h.
Compared with prior art, the features of the present invention and advantageous effect are：
The present invention keeps dispersion of the carbon in magnesia carbon brick matrix more uniform, is filled in granularity by quoting a kind of nano-sized carbon In different magnesia internal voids and crystal grain gap, to reduce the porosity of final products, increase the consistency of product and strong The performances such as degree.Meanwhile the stress generated when the also absorbable refractory material expanded by heating of nano-sized carbon and cooling contraction, it is answered to reduce Power crackle improves the thermal shock resistance of product.
Compared with existing inventive technique, the present invention has following advantage：Total carbon needed for product can reduce half, both save Cost of material, and extend the service life of magnesia carbon brick；In addition, manufacturing cost of the present invention is low, and it is simple for process, it is suitable for industrialization It is promoted using with a wide range of.
Specific implementation mode
Below by specific embodiment, the present invention is further illustrated, is not the restriction to its protection domain.
To exempt to repeat, Unify legislation is made to fixed raw material in following embodiment and identical technique：
Magnesia MgO mass accountings >=97%, CaO/SiO used2Mass ratio >=2, granularity≤10mm.Grading is：5mm ~3mm, 20%~30% (w)；3mm~1mm, 20%~25% (w)；1mm~0.088mm, 20%~30% (w)；It is less than 0.088mm~5mm, 10%~20% (w).Bonding agent used is industrial liquid phenolic resin.
Embodiment 1
The low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present embodiment, raw material mass mixture ratio are：90% (magnesia particle of magnesia 60%, magnesia powder 30%), nano carbon black 2.5%, antioxidant aluminium powder (purity >=98%, granularity≤100 μm) 3.5%, phenol Urea formaldehyde 4%.
Preparation method follows the steps below：
(1) dispensing is in mass ratio：Magnesia 90% (magnesia particle 60%, magnesia powder 30%), resists nano carbon black 2.5% Oxidant aluminium powder (purity >=98%, granularity≤100 μm) 3.5%, phenolic resin 4% configure raw material；
(2) batch mixing：Batch mixing in the following order：Magnesia particle mill mixes 2min, then plus nano oxidized graphite flake, aluminium powder mill mix 5min, then phenolic resin mill is added to mix 5min, finally plus magnesia powder mill mixes 10min；
(3) compression moulding and drying：The mixed uniform raw material of mill is pressed into electric screw press at 150MPa 200mm × 50mm × 50mm square bricks, dry 10h is got product at 120 DEG C.
After testing, the parameters of made low carbon magnesia carbon brick are as follows：Aobvious porosity is 4.2%~4.4%, and bulk density is 3.05g·cm-3~3.08gcm-3；Room temperature compression strength is 42MPa~45MPa；Using Static crucible method, steel converter is used Slag keeps the temperature 4h at 1650 DEG C, and penetration depth is 3.1mm~3.3mm.
Embodiment 2
The low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present embodiment, raw material mass mixture ratio are：90% (magnesia particle of magnesia 65%, magnesia powder 25%), nano carbon black 3.5%, antioxidant silica flour (purity >=98%, granularity≤100 μm) 2.5%, phenol Urea formaldehyde 4%.
Preparation method follows the steps below：
(1) dispensing is in mass ratio：Magnesia 90% (magnesia particle 65%, magnesia powder 25%), resists nano carbon black 3.5% Oxidant silica flour (purity >=98%, granularity≤100 μm) 2.5%, phenolic resin 4% configure raw material；
(2) batch mixing：Magnesia particle mill mixes 2min, then plus nano carbon black, silica flour mill mix 5min, then adds phenolic resin mill mixed 5min, finally plus magnesia powder mill mixes 10min；
(3) compression moulding and drying：The mixed uniform raw material of mill is pressed into electric screw press at 120MPa 200mm × 50mm × 50mm square bricks, dry 10h is got product at 120 DEG C.
After testing, the parameters of made low carbon magnesia carbon brick are as follows：Aobvious porosity is 4.1%~4.3%, and bulk density is 3.09g·cm-3~3.12gcm-3；Room temperature compression strength is 47MPa~50MPa；Using Static crucible method, steel converter is used Slag keeps the temperature 4h at 1650 DEG C, and penetration depth is 2.6mm~2.9mm.
Embodiment 3
The low carbon magnesia carbon brick of the nano-sized carbon enhancing of the present embodiment, raw material mass mixture ratio are：90% (magnesia particle of magnesia 60%, magnesia powder 30%), carbon nanotube 2%, nano carbon black 1%, antioxidant aluminium powder (purity >=98%, the μ of granularity≤100 M) 3%, phenolic resin 4%.
Preparation method follows the steps below：
(1) dispensing is in mass ratio：Magnesia 90% (magnesia particle 60%, magnesia powder 30%), carbon nanotube 2%, nanometer Carbon black 1%, antioxidant aluminium powder (purity >=98%, granularity≤100 μm) 3%, phenolic resin 4% configure raw material；
(2) batch mixing：Magnesia particle mill mixes 2min, then carbon nanotube, nano carbon black, aluminium powder mill is added to mix 5min, then add phenolic aldehyde Resin mill mixes 5min, and finally plus magnesia powder mill mixes 10min；
(3) compression moulding and drying：.The mixed uniform raw material of mill is pressed into electric screw press at 180MPa 200mm × 50mm × 50mm square bricks, dry 10h is got product at 120 DEG C.
After testing, the parameters of made low carbon magnesia carbon brick are as follows：Aobvious porosity is 3.9%~4.3%, and bulk density is 3.01g·cm-3~3.0.8gcm-3；Room temperature compression strength is 39MPa~48MPa；Using Static crucible method, steel converter is used Slag keeps the temperature 4h at 1650 DEG C, and penetration depth is 2.4mm~3.1mm.

Claims (10)

1. a kind of low carbon magnesia carbon brick of nano-sized carbon enhancing, it is characterised in that according to mass percent, raw material magnesia 90%~95%, Nano-sized carbon 2~4%, antioxidant 2%~3%, bonding agent 4%.
2. a kind of preparation method of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention as described in claim 1, feature exist In following the steps below：
(1) dispensing：In mass ratio, magnesia 90%~95%, nano-sized carbon 2~4%, antioxidant 2%~3%, bonding agent 4% into Row dispensing；
(2) it is kneaded：By above-mentioned dispensing according to certain sequence the mixing in batch mixer；
(3) it suppresses：By the forcing press compression moulding of the powder of mixing；
(4) dry：The magnesia carbon brick green compact pressed are dried in drying box to get finished product.
3. a kind of preparation method of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2, feature It is that the magnesia is fused magnesite, wherein MgO mass accounting >=97%, CaO/SiO2Mass ratio >=2, granularity≤10mm.
4. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~3 any one Method, it is characterised in that carbonaceous amount accounting >=98% in the nano-sized carbon, be nano oxidized graphite flake, carbon nanotube, carbon black, Activated carbon, coke or in which two kinds of arbitrary ratio mixing.
5. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~4 any one Method, it is characterised in that the antioxidant is Ca, Si, Al, SiC, Si3N4One of which, granularity≤200 μm.
6. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~5 any one Method, it is characterised in that the bonding agent is one kind of phenolic resin, synthetic resin, magnalium cementing agent.
7. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~6 any one Method, it is characterised in that batch mixing sequence is：Magnesia, nano-sized carbon, antioxidant, bonding agent and the magnesium of big granularity and middle granularity Sand fine powder, mixing time is using 5min~10min as interval.
8. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~7 any one Method, it is characterised in that pressure when the described compression moulding is 100MPa~300MPa.
9. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~8 any one Method, it is characterised in that the drying temperature is 100 DEG C~300 DEG C.
10. a kind of preparation of the low carbon magnesia carbon brick of the nano-sized carbon enhancing of present invention according to claim 2~9 any one Method, it is characterised in that the heat treatment time is 8h~12h.
CN201810613284.XA 2018-06-14 2018-06-14 A kind of low carbon magnesia carbon brick and preparation method thereof of nano-sized carbon enhancing Pending CN108484130A (en)

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN109836136A (en) * 2019-03-08 2019-06-04 河南竹林庆州耐火材料有限公司 A kind of low-carbon aluminium-magnesia carbon brick and preparation method thereof
CN111348897A (en) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 Method for improving strength of low-carbon magnesium-carbon material
CN111348902A (en) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 Method for improving oxidation resistance of low-carbon magnesia carbon material
CN111348899A (en) * 2019-07-08 2020-06-30 营口石兴耐火材料科技有限公司 Method for enhancing thermal shock resistance of low-carbon magnesia-carbon material
CN111732418A (en) * 2020-08-28 2020-10-02 北京利尔高温材料股份有限公司 Ultra-low carbon magnesia carbon brick for stainless steel ladle bottom and preparation method thereof
CN112028613A (en) * 2020-09-02 2020-12-04 江苏苏嘉集团新材料有限公司 Magnesia carbon brick using catalyst-added phenolic resin
CN112456976A (en) * 2020-12-07 2021-03-09 海城利尔麦格西塔材料有限公司 Low-carbon magnesia carbon brick and preparation method thereof
CN113248269A (en) * 2021-05-17 2021-08-13 江苏苏嘉集团新材料有限公司 Magnesia carbon brick added with composite binder and preparation method thereof
CN113754410A (en) * 2021-09-03 2021-12-07 江苏锦耐新材料科技有限公司 Low-carbon microporous magnesia carbon brick and preparation method thereof
CN114573325A (en) * 2022-03-25 2022-06-03 中冶武汉冶金建筑研究院有限公司 Low-carbon magnesia carbon brick and preparation method thereof

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836136A (en) * 2019-03-08 2019-06-04 河南竹林庆州耐火材料有限公司 A kind of low-carbon aluminium-magnesia carbon brick and preparation method thereof
CN111348897A (en) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 Method for improving strength of low-carbon magnesium-carbon material
CN111348902A (en) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 Method for improving oxidation resistance of low-carbon magnesia carbon material
CN111348899A (en) * 2019-07-08 2020-06-30 营口石兴耐火材料科技有限公司 Method for enhancing thermal shock resistance of low-carbon magnesia-carbon material
CN111732418B (en) * 2020-08-28 2020-12-18 北京利尔高温材料股份有限公司 Ultra-low carbon magnesia carbon brick for stainless steel ladle bottom and preparation method thereof
CN111732418A (en) * 2020-08-28 2020-10-02 北京利尔高温材料股份有限公司 Ultra-low carbon magnesia carbon brick for stainless steel ladle bottom and preparation method thereof
CN112028613A (en) * 2020-09-02 2020-12-04 江苏苏嘉集团新材料有限公司 Magnesia carbon brick using catalyst-added phenolic resin
CN112028613B (en) * 2020-09-02 2022-07-19 江苏苏嘉集团新材料有限公司 Magnesia carbon brick using catalyst-added phenolic resin
CN112456976A (en) * 2020-12-07 2021-03-09 海城利尔麦格西塔材料有限公司 Low-carbon magnesia carbon brick and preparation method thereof
CN113248269A (en) * 2021-05-17 2021-08-13 江苏苏嘉集团新材料有限公司 Magnesia carbon brick added with composite binder and preparation method thereof
CN113248269B (en) * 2021-05-17 2023-02-14 江苏苏嘉集团新材料有限公司 Magnesia carbon brick added with composite binder and preparation method thereof
CN113754410A (en) * 2021-09-03 2021-12-07 江苏锦耐新材料科技有限公司 Low-carbon microporous magnesia carbon brick and preparation method thereof
CN113754410B (en) * 2021-09-03 2023-02-03 江苏锦耐新材料科技有限公司 Low-carbon microporous magnesia carbon brick and preparation method thereof
CN114573325A (en) * 2022-03-25 2022-06-03 中冶武汉冶金建筑研究院有限公司 Low-carbon magnesia carbon brick and preparation method thereof

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Application publication date: 20180904