CN106187243A - A kind of cement kiln spinel refractory and preparation method thereof - Google Patents

A kind of cement kiln spinel refractory and preparation method thereof Download PDF

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CN106187243A
CN106187243A CN201610581954.5A CN201610581954A CN106187243A CN 106187243 A CN106187243 A CN 106187243A CN 201610581954 A CN201610581954 A CN 201610581954A CN 106187243 A CN106187243 A CN 106187243A
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cement kiln
content
preparation
spinel refractory
granularity
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CN106187243B (en
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王周福
赵顺
姜鹏程
刘浩
王玺堂
马妍
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Wuhan University of Science and Engineering WUSE
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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
    • 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
    • C04B35/44—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 aluminates
    • C04B35/443—Magnesium aluminate spinel
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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
    • C04B2235/32—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
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
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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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

The present invention relates to a kind of cement kiln spinel refractory and preparation method thereof.Its technical scheme is: by aluminum-containing raw material, spinelle, magnesia, magnesium salt, containing rare earths material, surfactant, additive and containing aluminum solutions mix, ball milling, obtain mixed slurry.By aluminum-containing raw material, zinc-containing raw materials, mix containing rare earths material, titaniferous materials and magnesium salt, ball milling, molding, heat treatment in reducing atmosphere；Successively in mixed slurry with containing vacuum impregnation in aluminum solutions, then heat treatment, grind, screening, obtain the different A material of granularity and B material.Spinelle, magnesia, corundum, A material, B material, zinc-containing raw materials, magnesium salt and mixed slurry are mixed, molding；Successively in 800 ~ 1200 DEG C and 1400 ~ 1700 DEG C of heat treatments, obtain the low heat conduction spinel refractory of high temperature.Raw material sources of the present invention are extensive, and production cost is low；The cement kiln spinel refractory intensity of preparation is high, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.

Description

A kind of cement kiln spinel refractory and preparation method thereof
Technical field
The invention belongs to spinel refractory technical field.It is specifically related to a kind of cement kiln spinel fire proofed wood Material and preparation method thereof.
Background technology
Magnesium aluminate spinel because having that fusing point is high, hardness big, thermal shock resistance and the excellent feature of resistance to slag corrosion, thus by extensively General for refractories industry.In recent years, people recognize Cr6+Harm, it is considered to spinel refractory is applied to water Mud rotary kiln, glass furnace and refining equipment etc. are to replace chromate-containing materials.But, due to spinel refractory elevated temperature strength The problem that low and erosion-resisting characteristics aspect exists, limits spinel refractory extensively should at above-mentioned industrial circle With.
In prior art, people are by introducing additive acceleration of sintering, but often generate a large amount of high-temperature liquid-phase, will weaken The character such as the thermal shock resistance of material and high temperature creep-resisting, reduce service life.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is therefore an objective to provide a kind of raw material sources extensively and production cost is low The preparation method of cement kiln spinel refractory；The cement kiln spinel refractory intensity prepared by the method High, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.
For achieving the above object, the technical solution used in the present invention is:
The first step, by the aluminum-containing raw material of 20 ~ 40wt%, the spinelle of 1 ~ 10wt%, the magnesia of 10 ~ 20wt%, the magnesium salt of 1 ~ 10wt%, The mixing containing aluminum solutions containing rare earths material, the surfactant of 1 ~ 10wt%, the additive of 1 ~ 10wt% and 30 ~ 60wt% of 1 ~ 10wt% Close uniformly, ball milling, obtain mixed slurry.
Second step, by the described aluminum-containing raw material of 20 ~ 40wt%, the zinc-containing raw materials of 1 ~ 10wt%, 20 ~ 40wt% described containing dilute Soil raw material, the titaniferous materials of 1 ~ 10wt% and the described magnesium salt mix homogeneously of 10 ~ 30wt%, ball milling, press under the conditions of 50 ~ 100MPa Make type, heat treatment 3 ~ 6 hours under the conditions of reducing atmosphere and 800 ~ 1300 DEG C；Then vacuum impregnation in described mixed slurry 2 ~ 6 hours, described containing aluminum solutions in vacuum impregnation 2 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1200 ~ 1500 DEG C, broken Broken, grind, screening, obtain the granularity A material less than 0.088mm and B material that granularity is 0.088 ~ 3mm.
3rd step, by the described spinelle of 20 ~ 40wt%, the described magnesia of 10 ~ 20wt%, the corundum of 10 ~ 20wt%, 1 ~ The described A material of 10wt%, the described B material of 1 ~ 10wt%, the described zinc-containing raw materials of 1 ~ 10wt%, 1 ~ 10wt% described magnesium salt and The described mixed slurry mix homogeneously of 1 ~ 10wt%, compressing under the conditions of 120 ~ 180MPa；Then in 800 ~ 1200 DEG C of conditions Lower heat treatment 3 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1400 ~ 1700 DEG C, obtain cement kiln spinel fire proofed wood Material.
The granularity of described aluminum-containing raw material is less than 0.088mm；Described aluminum-containing raw material is hydrated alumina or is aluminium hydroxide, water Close SiO in aluminium oxide2Content less than 0.3wt%, Al (OH) in aluminium hydroxide3Content more than 99wt%.
The granularity of described spinelle is less than 5mm；Described spinelle is for sintering spinelle or being electric smelting spinelle, described Al in spinelle2O3Content more than 68wt%.
The described granularity containing rare earths material is less than 0.088mm；Described is Samarium trihydroxide. or for Neodymium hydroxide containing rare earths material, Sm (OH) in Samarium trihydroxide.3Content more than 99wt%, Nd (OH) in Neodymium hydroxide3Content more than 99wt%.
The granularity of described zinc-containing raw materials is less than 0.088mm；Described zinc-containing raw materials is zinc carbonate or is zinc sulfate, in zinc carbonate ZnCO3Content more than 99wt%, ZnSO in zinc sulfate4Content more than 99wt%.
The granularity of described titaniferous materials is less than 0.088mm；Described titaniferous materials is metatitanic acid or is titanium dioxide, in metatitanic acid TiO(OH)2Content more than 99wt%, TiO in titanium dioxide2Content more than 99wt%.
The granularity of described magnesia is less than 5mm；Described magnesia is magnesite clinker or is fused magnesite, MgO in described magnesia Content is more than 96wt%.
The granularity of described magnesium salt is less than 0.088mm；Described magnesium salt is magnesium oxalate or is magnesium carbonate, MgC in magnesium oxalate2O4· 2H2The content of O is more than 99wt%, MgCO in magnesium carbonate3Content more than 99wt%.
The granularity of described corundum is less than 5mm；Described corundum is plate diamond spar or is Brown Alundum, Al in described corundum2O3Contain Amount is more than 96wt%.
Described surfactant is dodecyldimethylammonium hydroxide inner salt or is acrylic acid methyl ester..
Described additive is hydroxyethyl cellulose or is carboxymethyl cellulose.
Described is Alumina gel or the aqueous solution for polyaluminium chloride containing aluminum solutions, and the concentration containing aluminum solutions is 25-30wt%.
Described reducing atmosphere is hydrogen atmosphere or is carbon monoxide atmosphere.
Described vacuum-impregnated vacuum is 0.01 ~ 0.06MPa.
Owing to using technique scheme, the present invention compared with prior art has a following good effect:
Raw material sources of the present invention are extensive, and production cost is low；The present invention is by the atmosphere in each step, granularity, one-tenth The strict control of the operation such as type and heat treatment, not only improve between homogenizing and the various feed particles of different material granule is tight Contact, also provides proportional space for the formation of micro structure, thus prepared cement kiln spinel refractory intensity High, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.
Cement kiln spinel refractory prepared by the present invention: cold crushing strength is more than 100MPa；200~1400 DEG C heat conductivity be 2 ~ 3.5W/ (m K).
Therefore, the raw material sources of the present invention are extensive, and production cost is low；Prepared cement kiln spinel refractory Intensity is high, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, not the restriction to its protection domain.
For avoiding repeating, first by as follows to the material involved by this detailed description of the invention and vacuum Unify legislation, embodiment In repeat no more:
The granularity of described aluminum-containing raw material is less than 0.088mm；SiO in described hydrated alumina2Content less than 0.3wt%, described hydrogen Al (OH) in aluminium oxide3Content more than 99wt%.
The granularity of described spinelle is less than 5mm；Al in described spinelle2O3Content more than 68wt%.
Granularity containing rare earths material is less than 0.088mm；Sm (OH) in described Samarium trihydroxide.3Content more than 99wt%, described Nd (OH) in Neodymium hydroxide3Content more than 99wt%.
The granularity of described zinc-containing raw materials is less than 0.088mm；ZnCO in described zinc carbonate3Content more than 99wt%, described sulfur ZnSO in acid zinc4Content more than 99wt%.
The granularity of described titaniferous materials is less than 0.088mm；TiO (OH) in described metatitanic acid2Content more than 99wt%, institute State TiO in titanium dioxide2Content more than 99wt%.
The granularity of described magnesia is less than 5mm；In described magnesia, the content of MgO is more than 96wt%.
The granularity of described magnesium salt is less than 0.088mm；MgC in described magnesium oxalate2O4·2H2The content of O is more than 99wt%, described MgCO in magnesium carbonate3Content more than 99wt%.
The granularity of described corundum is less than 5mm；Al in described corundum2O3Content more than 96wt%.
The described concentration containing aluminum solutions is 25 ~ 30wt%.
Described reducing atmosphere is hydrogen atmosphere or carbon monoxide atmosphere.
Described vacuum-impregnated vacuum is 0.01-0.06MPa.
Embodiment 1
A kind of cement kiln spinel refractory and preparation method thereof.Described in the present embodiment, preparation method is:
The first step, by the aluminum-containing raw material of 20 ~ 30wt%, the spinelle of 1 ~ 10wt%, the magnesia of 10 ~ 20wt%, the magnesium salt of 1 ~ 10wt%, The mixing containing aluminum solutions containing rare earths material, the surfactant of 1 ~ 10wt%, the additive of 1 ~ 10wt% and 45 ~ 60wt% of 1 ~ 10wt% Close uniformly, ball milling, obtain mixed slurry.
Second step, by the described aluminum-containing raw material of 20 ~ 30wt%, the zinc-containing raw materials of 1 ~ 10wt%, 30 ~ 40wt% described containing dilute Soil raw material, the titaniferous materials of 1 ~ 10wt% and the described magnesium salt mix homogeneously of 10 ~ 30wt%, ball milling, press under the conditions of 50 ~ 100MPa Make type, heat treatment 3 ~ 6 hours under the conditions of reducing atmosphere and 800 ~ 1200 DEG C；Then vacuum impregnation in described mixed slurry 2 ~ 6 hours, described containing aluminum solutions in vacuum impregnation 2 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1200 ~ 1400 DEG C, broken Broken, grind, screening, obtain the granularity A material less than 0.088mm and B material that granularity is 0.088 ~ 3mm.
3rd step, by the described spinelle of 20 ~ 30wt%, the described magnesia of 15 ~ 20wt%, the corundum of 10 ~ 20wt%, 1 ~ The described A material of 10wt%, the described B material of 1 ~ 10wt%, the described zinc-containing raw materials of 1 ~ 10wt%, 1 ~ 10wt% described magnesium salt and The described mixed slurry mix homogeneously of 1 ~ 10wt%, compressing under the conditions of 120 ~ 180MPa；Then in 800 ~ 1100 DEG C of conditions Lower heat treatment 3 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1400 ~ 1600 DEG C, obtain cement kiln spinel fire proofed wood Material.
In the present embodiment:
Described aluminum-containing raw material is hydrated alumina；
Described spinelle is sintering spinelle；
Described is Samarium trihydroxide. containing rare earths material；
Described zinc-containing raw materials is zinc carbonate；
Described titaniferous materials is metatitanic acid；
Described magnesia is magnesite clinker；
Described magnesium salt is magnesium oxalate；
Described corundum is plate diamond spar；
Described surfactant is dodecyldimethylammonium hydroxide inner salt；
Described additive is hydroxyethyl cellulose；
Described is Alumina gel containing aluminum solutions；
Described reducing atmosphere is hydrogen atmosphere.
Embodiment 2
A kind of cement kiln spinel refractory and preparation method thereof.The present embodiment is remaining same embodiment in addition to following material 1:
Described aluminum-containing raw material is aluminium hydroxide；
Described spinelle is electric smelting spinelle；
Described is Neodymium hydroxide containing rare earths material；
Described zinc-containing raw materials is zinc sulfate；
Described titaniferous materials is titanium dioxide；
Described magnesia is fused magnesite；
Described magnesium salt is magnesium carbonate；
Described corundum is Brown Alundum；
Described surfactant is acrylic acid methyl ester.；
Described additive is carboxymethyl cellulose；
Described is the aqueous solution of polyaluminium chloride containing aluminum solutions；
Described reducing atmosphere is carbon monoxide atmosphere.
Embodiment 3
A kind of cement kiln spinel refractory and preparation method thereof.Described in the present embodiment, preparation method is:
The first step, by the aluminum-containing raw material of 30 ~ 40wt%, the spinelle of 1 ~ 10wt%, the magnesia of 10 ~ 20wt%, the magnesium salt of 1 ~ 10wt%, The mixing containing aluminum solutions containing rare earths material, the surfactant of 1 ~ 10wt%, the additive of 1 ~ 10wt% and 30 ~ 45wt% of 1 ~ 10wt% Close uniformly, ball milling, obtain mixed slurry.
Second step, by the described aluminum-containing raw material of 30 ~ 40wt%, the zinc-containing raw materials of 1 ~ 10wt%, 20 ~ 30wt% described containing dilute Soil raw material, the titaniferous materials of 1 ~ 10wt% and the described magnesium salt mix homogeneously of 10 ~ 30wt%, ball milling, press under the conditions of 50 ~ 100MPa Make type, heat treatment 3 ~ 6 hours under the conditions of reducing atmosphere and 900 ~ 1300 DEG C；Then vacuum impregnation in described mixed slurry 2 ~ 6 hours, described containing aluminum solutions in vacuum impregnation 2 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1300 ~ 1500 DEG C, broken Broken, grind, screening, obtain the granularity A material less than 0.088mm and B material that granularity is 0.088 ~ 3mm.
3rd step, by the described spinelle of 30 ~ 40wt%, the described magnesia of 10 ~ 15wt%, the corundum of 10 ~ 20wt%, 1 ~ The described A material of 10wt%, the described B material of 1 ~ 10wt%, the described zinc-containing raw materials of 1 ~ 10wt%, 1 ~ 10wt% described magnesium salt and The described mixed slurry mix homogeneously of 1 ~ 10wt%, compressing under the conditions of 120 ~ 180MPa；Then in 900 ~ 1200 DEG C of conditions Lower heat treatment 3 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1500 ~ 1700 DEG C, obtain cement kiln spinel fire proofed wood Material.
In the present embodiment:
Described aluminum-containing raw material is hydrated alumina；
Described spinelle is sintering spinelle；
Described is Samarium trihydroxide. containing rare earths material；
Described zinc-containing raw materials is zinc carbonate；
Described titaniferous materials is metatitanic acid；
Described magnesia is magnesite clinker；
Described magnesium salt is magnesium oxalate；
Described corundum is plate diamond spar；
Described surfactant is dodecyldimethylammonium hydroxide inner salt；
Described additive is hydroxyethyl cellulose；
Described is Alumina gel containing aluminum solutions；
Described reducing atmosphere is hydrogen atmosphere.
Embodiment 4
A kind of cement kiln spinel refractory and preparation method thereof.The present embodiment is remaining same embodiment in addition to following material 3:
Described aluminum-containing raw material is aluminium hydroxide；
Described spinelle is electric smelting spinelle；
Described is Neodymium hydroxide containing rare earths material；
Described zinc-containing raw materials is zinc sulfate；
Described titaniferous materials is titanium dioxide；
Described magnesia is fused magnesite；
Described magnesium salt is magnesium carbonate；
Described corundum is Brown Alundum；
Described surfactant is acrylic acid methyl ester.；
Described additive is carboxymethyl cellulose；
Described is the aqueous solution of polyaluminium chloride containing aluminum solutions；
Described reducing atmosphere is carbon monoxide atmosphere.
This detailed description of the invention compared with prior art has a following good effect:
The raw material sources that this detailed description of the invention is used are extensive, and production cost is low；This detailed description of the invention is by each step In the strict control of the operation such as atmosphere, granularity, molding and heat treatment, not only improve the homogenizing of different material granule and various former Close contact between material granule, also the formation for micro structure provides proportional space, thus prepared cement kiln point is brilliant Stone fire resistant materials intensity is high, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.
Cement kiln spinel refractory prepared by this detailed description of the invention: cold crushing strength is more than 100MPa； Heat conductivity in the range of 200 ~ 1400 DEG C is 2 ~ 3.5W/ (m K).
Therefore, the raw material sources of this detailed description of the invention are extensive, and production cost is low；Prepared cement kiln spinel Refractory material intensity is high, corrosion resistance is excellent, thermal shock resistance is high and heat conductivity is low.

Claims (10)

1. the preparation method of a cement kiln spinel refractory, it is characterised in that the concrete steps of described preparation method It is:
The first step, by the aluminum-containing raw material of 20 ~ 40wt%, the spinelle of 1 ~ 10wt%, the magnesia of 10 ~ 20wt%, the magnesium salt of 1 ~ 10wt%, The mixing containing aluminum solutions containing rare earths material, the surfactant of 1 ~ 10wt%, the additive of 1 ~ 10wt% and 30 ~ 60wt% of 1 ~ 10wt% Close uniformly, ball milling, obtain mixed slurry；
Second step, by the described aluminum-containing raw material of 20 ~ 40wt%, the zinc-containing raw materials of 1 ~ 10wt%, 20 ~ 40wt% described former containing rare earth Material, the titaniferous materials of 1 ~ 10wt% and the described magnesium salt mix homogeneously of 10 ~ 30wt%, ball milling, be pressed under the conditions of 50 ~ 100MPa Type, heat treatment 3 ~ 6 hours under the conditions of reducing atmosphere and 800 ~ 1300 DEG C；Then vacuum impregnation 2 ~ 6 in described mixed slurry Hour, described containing aluminum solutions in vacuum impregnation 2 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1200 ~ 1500 DEG C, broken, Grind, screening, obtain the granularity A material less than 0.088mm and B material that granularity is 0.088 ~ 3mm；
3rd step, by the described spinelle of 20 ~ 40wt%, the described magnesia of 10 ~ 20wt%, the corundum of 10 ~ 20wt%, 1 ~ 10wt% Described A material, the described B material of 1 ~ 10wt%, the described zinc-containing raw materials of 1 ~ 10wt%, the described magnesium salt of 1 ~ 10wt% and 1 ~ 10wt% Described mixed slurry mix homogeneously, compressing under the conditions of 120 ~ 180MPa；Then under the conditions of 800 ~ 1200 DEG C at heat Manage 3 ~ 6 hours, heat treatment 3 ~ 6 hours under the conditions of 1400 ~ 1700 DEG C, obtain cement kiln spinel refractory；
The granularity of described aluminum-containing raw material is less than 0.088mm；Described aluminum-containing raw material is hydrated alumina or aluminium hydroxide, aqua oxidation SiO in aluminum2Content less than 0.3wt%, Al (OH) in aluminium hydroxide3Content more than 99wt%；
The granularity of described spinelle is less than 5mm；Described spinelle is sintering spinelle or electric smelting spinelle, in described spinelle Al2O3Content more than 68wt%；
The described granularity containing rare earths material is less than 0.088mm；Described is Samarium trihydroxide. or Neodymium hydroxide containing rare earths material, hydroxide Sm (OH) in samarium3Content more than 99wt%, Nd (OH) in Neodymium hydroxide3Content more than 99wt%；
The granularity of described zinc-containing raw materials is less than 0.088mm；Described zinc-containing raw materials is zinc carbonate or zinc sulfate, ZnCO in zinc carbonate3's Content is more than 99wt%, ZnSO in zinc sulfate4Content more than 99wt%；
The granularity of described titaniferous materials is less than 0.088mm；Described titaniferous materials is metatitanic acid or titanium dioxide, TiO in metatitanic acid (OH)2Content more than 99wt%, TiO in titanium dioxide2Content more than 99wt%.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described magnesia For magnesite clinker or be fused magnesite, in described magnesia, the content of MgO is more than 96wt%；The granularity of described magnesia is less than 5mm.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described magnesium salt For magnesium oxalate or be magnesium carbonate, MgC in magnesium oxalate2O4·2H2The content of O is more than 99wt%, MgCO in magnesium carbonate3Content be more than 99wt%；The granularity of described magnesium salt is less than 0.088mm.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described corundum For plate diamond spar or be Brown Alundum, Al in described corundum2O3Content more than 96wt%；The granularity of described corundum is less than 5 mm.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described surface Activating agent is dodecyldimethylammonium hydroxide inner salt or is acrylic acid methyl ester..
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described interpolation Agent is hydroxyethyl cellulose or is carboxymethyl cellulose.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described containing aluminum Solution is Alumina gel or the aqueous solution for polyaluminium chloride, and the concentration containing aluminum solutions is 25 ~ 30wt%.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described reduction Atmosphere is hydrogen atmosphere or is carbon monoxide atmosphere.
The preparation method of cement kiln spinel refractory the most according to claim 1, it is characterised in that described vacuum The vacuum of dipping is 0.01 ~ 0.06MPa.
10. a cement kiln spinel refractory, it is characterised in that described cement kiln spinel refractory is According to the cement kiln prepared by the preparation method of cement kiln spinel refractory according to any one of claim 1 ~ 9 Use spinel refractory.
CN201610581954.5A 2016-07-22 2016-07-22 A kind of cement kiln spinel refractory and preparation method thereof Expired - Fee Related CN106187243B (en)

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CN107324796A (en) * 2017-06-15 2017-11-07 西安建筑科技大学 A kind of carbon/magnesium aluminate spinel composite powder
CN111348928A (en) * 2020-04-23 2020-06-30 无锡市南方耐材有限公司 Filling fire clay for assembling tundish upper nozzle iron shell and preparation method thereof
CN113788693A (en) * 2021-10-12 2021-12-14 浙江锦诚新材料股份有限公司 Coal injection pipe prefabricated part for cement kiln and preparation method thereof
CN113816726A (en) * 2021-09-03 2021-12-21 山东柯信新材料有限公司 Novel steel tapping hole and preparation method

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CN111348928A (en) * 2020-04-23 2020-06-30 无锡市南方耐材有限公司 Filling fire clay for assembling tundish upper nozzle iron shell and preparation method thereof
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CN113816726A (en) * 2021-09-03 2021-12-21 山东柯信新材料有限公司 Novel steel tapping hole and preparation method
CN113816726B (en) * 2021-09-03 2023-01-10 山东柯信新材料有限公司 Steel tapping hole and preparation method
CN113788693A (en) * 2021-10-12 2021-12-14 浙江锦诚新材料股份有限公司 Coal injection pipe prefabricated part for cement kiln and preparation method thereof
CN113788693B (en) * 2021-10-12 2023-11-28 浙江锦诚新材料股份有限公司 Coal injection pipe prefabricated member for cement kiln and preparation method thereof

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