CN110194673A - A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof - Google Patents

A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof Download PDF

Info

Publication number
CN110194673A
CN110194673A CN201910472476.8A CN201910472476A CN110194673A CN 110194673 A CN110194673 A CN 110194673A CN 201910472476 A CN201910472476 A CN 201910472476A CN 110194673 A CN110194673 A CN 110194673A
Authority
CN
China
Prior art keywords
energy
saving
zirconium oxide
mullite
refractory material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910472476.8A
Other languages
Chinese (zh)
Inventor
向若飞
李远兵
李淑静
王海路
周子孟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WUXI YIGANG NAIHUO MATERIAL Co.,Ltd.
Original Assignee
Wuhan University of Science and Engineering WUSE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Science and Engineering WUSE filed Critical Wuhan University of Science and Engineering WUSE
Priority to CN201910472476.8A priority Critical patent/CN110194673A/en
Publication of CN110194673A publication Critical patent/CN110194673A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16Shaped 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 silicates other than clay
    • C04B35/18Shaped 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 silicates other than clay rich in aluminium oxide
    • C04B35/185Mullite 3Al2O3-2SiO2
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227Lanthanum oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232Titanium oxides or titanates, e.g. rutile or anatase
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74Physical characteristics
    • C04B2235/77Density
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient

Abstract

The present invention relates to a kind of energy-saving mullite zirconium oxide multiple phase refractory materials and preparation method thereof.Its technical solution is: by Al2O3∶SiO2Mass ratio be (2.55~2.85): 1, zircon tailing and alumina are mixed to get mixture;The water of the titanium oxide of the additional 3~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and 30~40wt%, 5~7h of ball milling obtain ball milling material again;Then dry by the ball milling material extrusion molding, 4~8 hours are kept the temperature under the conditions of 1550~1650 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.The present invention has the characteristics that production cost is low, environmental pollution is small and easy to industrialized production.The prepared lower thermal expansion coefficient of mullite zirconium oxide multiple phase refractory material is low, energy-saving effect is good and use scope is wide.

Description

A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof
Technical field
The invention belongs to technical field of refractory materials.More particularly to a kind of energy-saving mullite zirconium oxide multiple phase refractory material And preparation method thereof.
Background technique
Mullite has many advantages, such as thermal expansion coefficient is small, refractoriness is high and electrical insulating property is strong, is widely used in fire resisting The industries such as material, chemistry and electric power.Zirconium oxide has different crystal phases, and monocline crystal phase is stablized at 1170 DEG C hereinafter, tetragonal phase Stablize between 1170~2570 DEG C, cubic phase is stablized between 2570~2680 DEG C (fusing points).In the preparation of mullite Zirconium oxide is introduced in journey, and the mechanical property of material can be greatly improved using the transformation toughening of zirconium oxide.
Zircon tailing is the solid waste generated in zircon exploitation and ore dressing process, utilizes zircon tailing system The standby mullite material containing zirconium oxide can not only reduce production cost, improves mineral products utilization efficiency and alleviate current mineral resources Nervous situation, and can be reduced environmental pollution caused by tailing, there is good social value and economic value.
" a method of mullite powder is prepared by raw material of flyash " (ZL201210255167.3) and " modified kaolin The method of low temperature preparation mullite " (ZL201210104659.2) patented technology, though mullite material is made, major defect exists In: high production cost and production technology are complicated, are unfavorable for accomplishing scale production;Using fluorochemical, environmental pollution is caused. " a kind of mullite lightweight thermal insulation brick and preparation method thereof based on discarded molding sand " (ZL201210105340.1), " one kind contains zirconium Cordierite composite diphase material and preparation method thereof " (ZL201410522759.6), " one kind composite diphase material containing zirconium mullite and its preparation Method " (ZL201410522993.9) and " one kind is containing zirconium mullite-vagcor composite diphase material and preparation method thereof " (201410523197.7) patented technology, though above-mentioned technology using hot investment casting discarded molding sand be made mullite lightweight thermal insulation brick, Cordierite containing zirconium contains zirconium mullite and vagcor containing zirconium mullite, and major defect is discarded molding sand from metal casting Industry is made, a large amount of metals contained therein and metal oxide weaken high-temperature behavior.It is " a kind of to produce mullite using flyash Method " (ZL201210005536.3) patented technology, though the technology using pre-treating fly ash as raw material be fired to obtain come Stone can generate a large amount of waste water in production process.
Summary of the invention
The present invention is directed to overcome prior art defect, it is therefore an objective to it is low, environmental-friendly and be easy to work to provide a kind of production cost The preparation method for the mullite zirconium oxide multiple phase refractory material that industry metaplasia produces.The energy-saving mullite oxidation prepared by this method The thermal expansion coefficient of zirconium multiple phase refractory material is low, energy-saving effect is good and use scope is wide.
To achieve the above object, the technical solution adopted by the present invention is that:
By Al2O3∶SiO2Mass ratio be (2.55~2.85): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 30~40wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1550~ 4~8 hours are kept the temperature under the conditions of 1650 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
The zircon tailing: Al2O3Content is 40~60wt%, SiO2Content is 30~50wt%, ZrO2Content >= 7wt%;Partial size≤0.15mm of the zircon tailing.
The alumina: Al2O3Content is 80~85wt%, SiO2Content is 10~15wt%;The partial size of the alumina≤ 0.089mm。
The TiO of the titanium oxide2Content >=95wt%;Partial size≤0.06mm of titanium oxide.
The La of the lanthana2O3Content >=99.9wt%;Partial size≤0.04mm of lanthana.
Due to the adoption of the above technical scheme, the present invention has following good effect compared with prior art:
The section suitable for related fieldss such as refractory material and kiln furnitures is made using zircon tailing as primary raw material by the present invention Energy type mullite zirconium oxide multiple phase refractory material not only realizes solid waste resource recovery utilization, while reducing production cost With it is easy to industrialized production, and in process of production without harmful liquid generate, it is environmental-friendly.
Zircon high-temp in-situ in the zircon tailing that the present invention uses, which decomposes, generates zirconium oxide, is conducive to improve energy conservation The mechanical property of type mullite zirconium oxide multiple phase refractory material.The present invention is using caused by kyanite decomposition in zircon tailing Volume expansion forms stomata in energy-saving mullite zirconium oxide multiple phase refractory material, reduces accumulation of heat, reaches energy-efficient purpose.
The present invention can not only reduce the heat treatment temperature of product, alleviate aquamaine in zircon tailing by introducing titanium oxide Cubic deformation caused by stone decomposes;Simultaneously by introducing lanthana, improve energy-saving mullite zirconium oxide multiple phase refractory material Liquid phase ingredient under high temperature improves its applied at elevated temperature effect.
Energy-saving mullite zirconium oxide multiple phase refractory material prepared by the present invention is through X-ray diffraction analysis: principal crystalline phase is not Carry out stone, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.4~2.8g/cm3;Apparent porosity be 13.9~ 18.1%;Fracture toughness is 3.1~4.7MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 4.81 × 10-6~5.79 × 10-6/℃。
Therefore, the present invention has the characteristics that production cost is low, environmental pollution is small and easy to industrialized production.It is prepared not The thermal expansion coefficient for carrying out stone zirconium oxide multiple phase refractory material is low, energy-saving effect is good and use scope is wide.
Specific embodiment
The present invention will be further described With reference to embodiment, not to the limit of the scope of the present invention System:
To avoid repeating.The technical parameter Unify legislation that first present embodiment to be related to is as follows, in embodiment It will not be described in great detail:
Partial size≤0.15mm of the zircon tailing.
Partial size≤0.089mm of the alumina.
The TiO of the titanium oxide2Content >=95wt%;Partial size≤0.06mm of titanium oxide.
The La of the lanthana2O3Content >=99.9wt%;Partial size≤0.04mm of lanthana.
Embodiment 1
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.55~2.65): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~4wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 30~33wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1550~ 7~8 hours are kept the temperature under the conditions of 1580 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 40~43wt%;SiO2Content is 47~50wt%;ZrO2Content is 7.0~7.2wt%.
The alumina: Al2O3Content is 80~81wt%;SiO2Content is 14~15wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.4~2.5g/cm3;Apparent porosity be 17.3~ 18.1%;Fracture toughness is 3.1~3.5MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 4.81~5.21 × 10-6/℃。
Embodiment 2
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.65~2.75): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 4~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 33~36wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1580~ 6~7 hours are kept the temperature under the conditions of 1610 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 43~46wt%;SiO2Content is 44~47wt%;ZrO2Content is 7.2~7.4wt%.
The alumina: Al2O3Content is 81~82wt%;SiO2Content is 13~14wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.5~2.6g/cm3;Apparent porosity be 16.5~ 17.4%;Fracture toughness is 3.5~3.9MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 4.95~5.32 × 10-6/℃。
Embodiment 3
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.75~2.85): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~4wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 36~39wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1610~ 5~6 hours are kept the temperature under the conditions of 1640 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 46~49wt%;SiO2Content is 41~44wt%;ZrO2Content is 7.4~7.6wt%.
The alumina: Al2O3Content is 82~83wt%;SiO2Content is 12~13wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.6~2.7g/cm3;Apparent porosity be 15.9~ 16.8%;Fracture toughness is 3.9~4.3MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.08~5.45 × 10-6/℃。
Embodiment 4
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.60~2.70): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 4~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 37~40wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1620~ 4~5 hours are kept the temperature under the conditions of 1650 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 49~52wt%;SiO2Content is 38~41wt%;ZrO2Content is 7.6~7.8wt%.
The Al of the alumina2O3Content is 83~84wt%;SiO2Content is 11~12wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.7~2.8g/cm3;Apparent porosity be 15.1~ 16.0%;Fracture toughness is 4.3~4.7MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.32~5.67 × 10-6/℃。
Embodiment 5
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.70~2.80): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~4wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 31~34wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1560~ 6.5~7.5 hours are kept the temperature under the conditions of 1590 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 52~55wt%;SiO2Content is 35~38wt%;ZrO2Content is 7.8~8.0wt%.
The alumina: Al2O3Content is 84~85wt%;SiO2Content is 10~11wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.5~2.6g/cm3;Apparent porosity be 16.9~ 17.7%;Fracture toughness is 3.2~3.6MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.33~5.69 × 10-6/℃。
Embodiment 6
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.55~2.65): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 4~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 34~37wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1590~ 5.5~6.5 hours are kept the temperature under the conditions of 1620 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 55~58wt%;SiO2Content is 32~35wt%;ZrO2Content is 8.0~8.2wt%.
The alumina: Al2O3Content is 80.5~81.5wt%;SiO2Content is 13.5~14.5wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis, principal crystalline phase prepared by the present embodiment For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.6~2.7g/cm3;Apparent porosity be 16.4~ 17.2%;Fracture toughness is 3.6~4.0MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.43~5.71 × 10-6/℃。
Embodiment 7
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.65~2.75): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~4wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 37~40wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1620~ 4.5~5.5 hours are kept the temperature under the conditions of 1650 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 57~60wt%;SiO2Content is 30~33wt%;ZrO2Content is 8.1~8.3wt%.
The alumina: Al2O3Content is 81.5~82.5wt%;SiO2Content is 12.5~13.5wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.7~2.8g/cm3;Apparent porosity be 14.7~ 15.5%;Fracture toughness is 4.1~4.5MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.49~5.71 × 10-6/℃。
Embodiment 8
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.75~2.85): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 4~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 32~35wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1570~ 7~8 hours are kept the temperature under the conditions of 1600 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 50~53wt%;SiO2Content is 37~40wt%;ZrO2Content is 8.2~8.4wt%.
The alumina: Al2O3Content is 82.5~83.5wt%;SiO2Content is 11.5~12.5wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis, principal crystalline phase prepared by the present embodiment For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.6~2.7g/cm3;Apparent porosity be 16.5~ 17.3%;Fracture toughness is 4.3~4.7MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.50~5.79 × 10-6/℃。
Embodiment 9
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.60~2.70): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 3~4wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 35~38wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1600~ 6~7 hours are kept the temperature under the conditions of 1630 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 52~55wt%;SiO2Content is 35~38wt%;ZrO2Content is 7.5~7.7wt%.
The alumina: Al2O3Content is 83.5~84.5wt%;SiO2Content is 10.5~11.5wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.7~2.8g/cm3;Apparent porosity be 14.2~ 15.1%;Fracture toughness is 3.8~4.2MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.10~5.41 × 10-6/℃。
Embodiment 10
A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof.Preparation method described in the present embodiment It is:
By Al2O3∶SiO2Mass ratio be (2.70~2.80): 1, zircon tailing and alumina are mixed to get mixing Material;Again the titanium oxide of the additional 4~5wt% of mixture, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and The water of 36~39wt%, 5~7h of ball milling obtain ball milling material;Then dry by the ball milling material extrusion molding, 1620~ 5~6 hours are kept the temperature under the conditions of 1650 DEG C, energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
In the present embodiment:
The zircon tailing: Al2O3Content is 54~57wt%;SiO2Content is 33~36wt%;ZrO2Content is 7.3~7.5wt%.
The alumina: Al2O3Content is 82~83wt%;SiO2Content is 12~13wt%.
Energy-saving mullite zirconium oxide multiple phase refractory material is through X-ray diffraction analysis prepared by the present embodiment: principal crystalline phase For mullite, secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.7~2.8g/cm3;Apparent porosity be 13.9~ 14.7%;Fracture toughness is 3.7~4.1MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 5.04~5.33 × 10-6/℃。
Present embodiment has following good effect compared with prior art:
Present embodiment, which is made using zircon tailing as primary raw material, is suitable for the correlations such as refractory material and kiln furnitures The energy-saving mullite zirconium oxide multiple phase refractory material in field not only realizes solid waste resource recovery utilization, reduces simultaneously Production cost and easy to industrialized production, and generated in process of production without harmful liquid, it is environmental-friendly.
The zircon high-temp in-situ in zircon tailing that present embodiment uses, which decomposes, generates zirconium oxide, is conducive to Improve the mechanical property of energy-saving mullite zirconium oxide multiple phase refractory material.Present embodiment utilizes indigo plant in zircon tailing Spar decomposes caused volume expansion, and stomata is formed in energy-saving mullite zirconium oxide multiple phase refractory material, reduces accumulation of heat, Reach energy-efficient purpose.
Present embodiment can not only reduce the heat treatment temperature of product, alleviate zircon tail by introducing titanium oxide Cubic deformation caused by kyanite decomposes in mine;Simultaneously by introducing lanthana, it is resistance to improve energy-saving mullite zirconium oxide complex phase Liquid phase ingredient at a high temperature of fiery material improves its applied at elevated temperature effect.
The energy-saving mullite zirconium oxide multiple phase refractory material of present embodiment preparation is through X-ray diffraction analysis: main Crystal phase is mullite, and secondary crystal phase is monoclinic zirconia.Through detecting: bulk density is 2.4~2.8g/cm3;Apparent porosity is 13.9 ~18.1%;Fracture toughness is 3.1~4.7MPam1/2;Thermal expansion coefficient (RT~1000 DEG C) is 4.81 × 10-6~5.79 × 10-6/℃。
Therefore, present embodiment has the characteristics that production cost is low, environmental pollution is small and easy to industrialized production.Institute The thermal expansion coefficient of the energy-saving mullite zirconium oxide multiple phase refractory material of preparation is low, energy-saving effect is good and use scope is wide.

Claims (6)

1. a kind of preparation method of energy-saving mullite zirconium oxide multiple phase refractory material, which is characterized in that press Al2O3∶SiO2Matter Amount is than being (2.55~2.85): 1, zircon tailing and alumina are mixed to get mixture;Again the additional mixture 3~ The titanium oxide of 5wt%, the lanthana of 0.6~0.8wt%, the polyvinyl alcohol of 4~6wt% and the water of 30~40wt%, ball milling 5~ 7h obtains ball milling material;Then dry by the ball milling material extrusion molding, 4~8 hours are kept the temperature under the conditions of 1550~1650 DEG C, Energy-saving mullite zirconium oxide multiple phase refractory material is made in natural cooling.
2. the preparation method of energy-saving mullite zirconium oxide multiple phase refractory material according to claim 1, it is characterised in that institute State zircon tailing: Al2O3Content is 40~60wt%, SiO2Content is 30~50wt%, ZrO2Content >=7wt%;The zirconium Partial size≤0.15mm of diamond stone tailing.
3. the preparation method of energy-saving mullite zirconium oxide multiple phase refractory material according to claim 1, it is characterised in that institute State alumina: Al2O3Content is 80~85wt%, SiO2Content is 10~15wt%;Partial size≤0.089mm of the alumina.
4. the preparation method of energy-saving mullite zirconium oxide multiple phase refractory material according to claim 1, it is characterised in that institute State the TiO of titanium oxide2Content >=95wt%;Partial size≤0.06mm of titanium oxide.
5. the preparation method of energy-saving mullite zirconium oxide multiple phase refractory material according to claim 1, it is characterised in that institute State the La of lanthana2O3Content >=99.9wt%;Partial size≤0.04mm of lanthana.
6. a kind of energy-saving mullite zirconium oxide multiple phase refractory material, it is characterised in that the energy-saving mullite zirconium oxide complex phase Refractory material be any one of according to claim 1~5 described in energy-saving mullite zirconium oxide multiple phase refractory material preparation Energy-saving mullite zirconium oxide multiple phase refractory material prepared by method.
CN201910472476.8A 2019-05-31 2019-05-31 A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof Pending CN110194673A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910472476.8A CN110194673A (en) 2019-05-31 2019-05-31 A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910472476.8A CN110194673A (en) 2019-05-31 2019-05-31 A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110194673A true CN110194673A (en) 2019-09-03

Family

ID=67753809

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910472476.8A Pending CN110194673A (en) 2019-05-31 2019-05-31 A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110194673A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112094128A (en) * 2020-09-25 2020-12-18 南阳开元高温新材料有限公司 High-strength mullite light heat-insulating brick
CN112125685A (en) * 2020-09-25 2020-12-25 南阳开元高温新材料有限公司 Low-heat-conduction mullite light heat-insulating brick
CN113105254A (en) * 2021-03-29 2021-07-13 彰武县联信铸造硅砂有限公司 Novel ceramic sand and preparation method thereof
CN113480300A (en) * 2021-07-13 2021-10-08 武汉科技大学 Mullite composite sagger and preparation method thereof
CN113511904A (en) * 2021-04-22 2021-10-19 武汉科技大学 Light-weight mullite refractory material and preparation method thereof
CN115124358A (en) * 2022-06-20 2022-09-30 北京金隅通达耐火技术有限公司 Microporous zirconium mullite raw material and preparation method and application thereof
CN116444279A (en) * 2022-01-06 2023-07-18 辽宁科技大学 Mullite whisker reinforced mullite composite material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121603A (en) * 2007-07-25 2008-02-13 濮阳濮耐高温材料(集团)股份有限公司 Method for preparing zirconium oxide/mullite crystal whisker multiple phase material
CN102424585A (en) * 2011-09-05 2012-04-25 中国地质大学(北京) Zirconia-mullite multiphase refractory raw material and preparation method thereof
CN102633512A (en) * 2012-04-12 2012-08-15 武汉科技大学 Abandoned molding sand based mullite light heat insulating bricks and preparation method thereof
CN104261810A (en) * 2014-10-08 2015-01-07 武汉科技大学 Zirconium-containing mullite composite phase material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121603A (en) * 2007-07-25 2008-02-13 濮阳濮耐高温材料(集团)股份有限公司 Method for preparing zirconium oxide/mullite crystal whisker multiple phase material
CN102424585A (en) * 2011-09-05 2012-04-25 中国地质大学(北京) Zirconia-mullite multiphase refractory raw material and preparation method thereof
CN102633512A (en) * 2012-04-12 2012-08-15 武汉科技大学 Abandoned molding sand based mullite light heat insulating bricks and preparation method thereof
CN104261810A (en) * 2014-10-08 2015-01-07 武汉科技大学 Zirconium-containing mullite composite phase material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
耿可明等人: "锆英石材料烧结性能研究", 《稀有金属材料与工程》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112094128A (en) * 2020-09-25 2020-12-18 南阳开元高温新材料有限公司 High-strength mullite light heat-insulating brick
CN112125685A (en) * 2020-09-25 2020-12-25 南阳开元高温新材料有限公司 Low-heat-conduction mullite light heat-insulating brick
CN112125685B (en) * 2020-09-25 2023-01-06 南阳开元高温新材料有限公司 Low-heat-conduction mullite light heat-insulating brick
CN113105254A (en) * 2021-03-29 2021-07-13 彰武县联信铸造硅砂有限公司 Novel ceramic sand and preparation method thereof
CN113105254B (en) * 2021-03-29 2022-10-21 彰武县联信铸造硅砂有限公司 Novel ceramic sand and preparation method thereof
CN113511904A (en) * 2021-04-22 2021-10-19 武汉科技大学 Light-weight mullite refractory material and preparation method thereof
CN113511904B (en) * 2021-04-22 2022-06-14 武汉科技大学 Light-weight mullite refractory material and preparation method thereof
CN113480300A (en) * 2021-07-13 2021-10-08 武汉科技大学 Mullite composite sagger and preparation method thereof
CN113480300B (en) * 2021-07-13 2023-07-21 武汉科技大学 Mullite composite sagger and preparation method thereof
CN116444279A (en) * 2022-01-06 2023-07-18 辽宁科技大学 Mullite whisker reinforced mullite composite material and preparation method thereof
CN115124358A (en) * 2022-06-20 2022-09-30 北京金隅通达耐火技术有限公司 Microporous zirconium mullite raw material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN110194673A (en) A kind of energy-saving mullite zirconium oxide multiple phase refractory material and preparation method thereof
CN102617171B (en) MgAlON combined aluminum magenisum permeable brick and preparation method thereof
CN106278321B (en) A kind of high tenacity refractory material and its preparation process
CN105503209B (en) A kind of mullite lightweight thermal insulation brick based on flint clay and preparation method thereof
CN106336200B (en) A kind of inorfil toughening refractory material and its preparation process
CN111620679A (en) Method for preparing high-purity mullite material by taking fused silica as silicon source
CN102583411A (en) Method for producing mullite by using fly ash
CN102219530B (en) Silicon mullite brick and preparation method thereof
CN102633512A (en) Abandoned molding sand based mullite light heat insulating bricks and preparation method thereof
CN101423375B (en) Ceramic roller and preparation method thereof
CN108689695A (en) The application process and its product obtained of a kind of aluminium ash in high alumina ceramic
CN103420684B (en) Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof
CN106336227B (en) A kind of mineral products waste refractory material and its preparation process
CN106278314B (en) A kind of intermediate frequency furnace coil clay and preparation method thereof
CN101585711A (en) Utilize useless mud of ceramics factory and commercial alumina to prepare the method for high alumina mullite aggregate
CN103351166B (en) Calcium hexaluminate/gehlenite diphase heat-insulation refractory material and preparation method thereof
CN105036167A (en) Calcium hexaluminate and preparation method thereof
CN104261810B (en) A kind of containing zirconium mullite composite diphase material and preparation method thereof
CN102424585A (en) Zirconia-mullite multiphase refractory raw material and preparation method thereof
CN102659448B (en) Zirconia special foam ceramic filter and preparation method thereof
CN108484161B (en) Aluminum titanate composite material and preparation method thereof
CN103304231A (en) Preparation method of microporous magnesium aluminate spinel raw material
CN112897994A (en) Preparation method of corundum spinel complex phase material
CN105948718A (en) Low-pore periclase-composite spinel bricks and preparation method therefor
CN105367047A (en) Preparation method of sintering body with principal crystalline phase of cordierite by using coal gangue and nickel slag

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20220420

Address after: 214226 Fangqian Village, Dingshu Town, Yixing City, Wuxi City, Jiangsu Province

Applicant after: WUXI YIGANG NAIHUO MATERIAL Co.,Ltd.

Address before: 430081 No. 947 Heping Avenue, Qingshan District, Hubei, Wuhan

Applicant before: WUHAN University OF SCIENCE AND TECHNOLOGY