CN109133854A - Method using red mud through roller kilns production split-phase furnace transmutation decoration composite material - Google Patents
Method using red mud through roller kilns production split-phase furnace transmutation decoration composite material Download PDFInfo
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- CN109133854A CN109133854A CN201811021063.XA CN201811021063A CN109133854A CN 109133854 A CN109133854 A CN 109133854A CN 201811021063 A CN201811021063 A CN 201811021063A CN 109133854 A CN109133854 A CN 109133854A
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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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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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
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
Abstract
The invention belongs to architectural pottery production technical fields, are specifically related to a kind of method using red mud through roller kilns production split-phase furnace transmutation decoration composite material.It using red mud, feldspar, vanadium titanium slag, quartz, borax, lepidolite and talcum as raw material, is put in Cinker clew furnace, the water quenching, broken and screened after 1400-1500 DEG C of melting takes sieve residue to be mixed, as split-phase transmutation raw material；It using feldspar, clay, flint clay, pyrophyllite and Wen Zushi as raw material, is put in ball mill, pellet is put in mold by mist projection granulating after ball milling 36h, and repressed molding obtains green body；By on split-phase transmutation raw material cloth to green body obtained, then, firing dry through roller kilns, i.e. production obtain split-phase furnace transmutation decoration composite material.The split-phase furnace transmutation decoration composite material that the present invention produces can satisfy all service performances and decorative performance of traditional ceramics, not use glaze colorant in production process, be a kind of green, environmental protection production technology.
Description
Technical field
The invention belongs to architectural pottery production technical field, it is specifically related to a kind of produce split-phase through roller kilns using red mud
The method of furnace transmutation decoration composite material.
Background technique
Recently as the continuous improvement of industrial level, the quantity of Chinese industrial products is increased substantially, thus Industrial Solid
The discharge quantity of body waste residue is very huge, wherein industrial by-products of the red mud as aluminium oxide, every annual emissions reach millions of
Ton or more, the annual discharge amount of schreyerite slag is also at 20,000,000 tons or more.The technology for developing and using these solid waste also exists
It continues to develop, but mainly concentrates on using them as the use in the low value-added direction such as roadbed packing material.And it is utilizing
Red mud as ceramic composite raw material in use, the variation of viscosity change and ferro element valence state is to pottery under its color, high temperature
Ingredient, production and the performance optimization of porcelain based composites bring detrimental effect.
Research using roller kilns fast stoving process production split-phase transmutation composite material is considerably less, and main problem is embodied in:
(1) split-phase glaze generally requires cloth twice, one layer of basestocks of first cloth, then one layer of split-phase raw material of cloth, utilizes two kinds
The difference of glaze viscosity at high temperature, the crystal phase for coming out split-phase generates transmutation effect, if only split-phase can be realized in one layered material of cloth
The production method of transmutation effect can increase substantially production efficiency, and ZL201210094756.8 discloses a kind of utilization lithium brightness
The raw materials such as stone, quartz, calcite, talcum, aluminium oxide, zinc oxide, sodium nitrate, zirconium English powder, bone ash, lithium carbonate and boric acid prepare base
Plinth crystalline glaze adds cerium oxide, nickel oxide, manganese dioxide, iron oxide, titanium dioxide, cobalt oxide or copper oxide as coloring
Agent, through roller kiln burning at the crystallite glass composite plate material based on spodumene, but its underlying crystal glaze and colorant are with chemical industry
Based on raw material, cost is excessively high, and the application field of product is restricted.Using solid waste, such as red mud and schreyerite slag, make
Production cost can be greatly lowered in the primary raw material for crystallizing transmutation for split-phase, but up to the present, by utilizing additive amount
Up to 50~60% red mud, the report through roller kilns production technology firing split-phase furnace transmutation decoration composite material are but not yet found.
(2) thermal expansion coefficient of solid green body and split-phase glaze has significant difference, must cloth when producing split-phase glazing type material
Otherwise the transition bed of material will make to produce obtained material to ensure the matching of thermal expansion coefficient between ceramic body and phase separation glaze
Bending, deformation or fracture.
(3) production process of split-phase kiln-transformation ceramic product needs accurate control firing temperature, is warming up to high temperature, again fast prompt drop first
Extremely lower temperature, and keep the temperature a period of time, it is therefore an objective to nucleus is first generated, then nucleus is made slowly to grow up, whole cycle needs 3~
5 hours, and on conventional roller kilns growth line, from firing is dried to the only 45 minutes time, to give birth in a short time
At nucleus, split-phase is grown up again, needs to further investigate and can realize on formula and technique.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide it is a kind of using red mud through roller kilns produce split-phase transmutation
The method of decorative composite material.Red mud dosage in split-phase transmutation raw material is big, and split-phase transmutation cost of material is low, is easy to industrial metaplasia
It produces；Producing obtained split-phase furnace transmutation decoration composite material can satisfy all service performances of traditional ceramics, also can satisfy biography
It unites the decorative performances of ceramics, does not use glaze colorant in production process, be greatly lowered because using glaze colorant due to bring mineral
Resource, the energy and labor cost are a kind of green, environmental protection production technologies.
It is of the present invention using red mud through roller kilns production split-phase furnace transmutation decoration composite material method, specifically include with
Lower step:
(1) preparation of split-phase transmutation raw material
It using red mud, feldspar, vanadium titanium slag, quartz, borax, lepidolite and talcum as raw material, is put in Cinker clew furnace, is passed through
It is water quenching after 1400-1500 DEG C of melting, broken and screened, take sieve residue to be mixed, as split-phase transmutation raw material；
(2) preparation of green body
It using feldspar, clay, flint clay, pyrophyllite and Wen Zushi as raw material, is put in ball mill, is sprayed after ball milling 36h
Mist is granulated, and pellet is put in mold, repressed molding obtains green body；
(3) preparation of split-phase furnace transmutation decoration composite material
On the green body that will be extremely obtained through step (2) through split-phase transmutation raw material cloth made from step (1), then through roller-way kiln drying
Dry, firing, i.e. production obtain split-phase furnace transmutation decoration composite material.
Wherein:
Preferably 1450 DEG C of melting temperature described in step (1).
It in step (1), is calculated in mass percent, raw material composition is as follows: red mud 50~60%, feldspar 7~10%, vanadium titanium slag
10~20%, quartz 10%, borax 6%, lepidolite 2~5% and talcum 2%.
Step mixes sieve residue described in (1), and by mass percentage, 8 mesh~10 mesh account in sieve residue
20%, 11 mesh~15 mesh account for 60%, and 15 mesh~20 mesh account for 20%.
It in step (2), is calculated in mass percent, raw material composition is as follows: feldspar 47%, clay 27%, flint clay 16%, leaf
Alabaster 5% and Wen Zu stone 5%.
Ratio of water to material in ball mill described in step (2) is 40:100；The pressure of the compression moulding is 200MPa.
To on split-phase transmutation raw material cloth to green body, be split-phase transmutation raw material described in step (3) by 4.7~7.8 kilograms/
Square metre cloth doses cloth to green body on.
Firing described in step (3), firing temperature be 1150~1170 DEG C, firing time be 65-75 minutes, preferably 70
Minute.
It is of the present invention multiple through roller kilns production split-phase furnace transmutation decoration using red mud as a preferred technical solution
The method of condensation material, specifically includes the following steps:
(1) ingredient: red mud 50~60%, feldspar 7~10%, vanadium titanium slag 10~20%, quartz is carried out by mass percentage
10%, borax 6%, lepidolite 2~5% and talcum 2%, are put in Cinker clew furnace, the water quenching, broken and through sieving after 1450 DEG C of meltings
Point, take sieve residue to be mixed by mass percentage, wherein 8 mesh~10 mesh account for 20%, 11 mesh~15 mesh account for 60%, 15 mesh~
20 mesh account for 20%, as split-phase transmutation raw material；
(2) ingredient: feldspar 47%, clay 27%, flint clay 16%, pyrophyllite 5% and Wen Zu is carried out by mass percentage
Stone 5%, is put in ball mill, ratio of water to material 40:100, and pellet is put in mold, through 200MPa by mist projection granulating after ball milling 36h
Compression moulding obtains green body；
(3) the cloth doses cloth of 4.7~7.8 kilograms/square metre will be pressed through split-phase transmutation raw material made from step (1) to through step
Suddenly on the green body that (2) obtain, then, firing dry through roller kilns, 1150~1170 DEG C of firing temperature, firing time is 70 minutes,
I.e. production obtains split-phase furnace transmutation decoration composite material.
Based on mass fraction, the ingredient of red mud described in step (1) is 34%Fe2O3, 24%Al2O3, 18%SiO2、
14%Na2O, 6.5%TiO2, 2.6%CaO, 0.7%S, 0.2%MgO, the ingredient of vanadium titanium slag is 27%CaO, 24%SiO2、
16%Al2O3, 9%MgO, 1.1%MnO, 1.8%FeO, 20%TiO2, 0.7%V2O5, 0.4%S.
Compared with the prior art, the present invention has the following beneficial effects:
(1) red mud dosage in split-phase transmutation raw material is big, and split-phase transmutation cost of material is low, easy to industrialized production.
(2) production technology is the roller kilns production technology of traditional ceramics, and composition of raw materials is adapted to the energy of traditional ceramics technique
Power is strong, and firing period is short, and the cost of split-phase furnace transmutation decoration composite material can be greatly lowered, and improves the benefit of production unit.
(3) the split-phase furnace transmutation decoration composite material that primary cloth can produce on green body, split-phase transmutation crystallization
Layer is between green body and surface transparent glass layer, and crystalline substance flower is metallochrome or brown, and get on, shape similar to fish scale from the appearance
Shape, size and distribution can be regulated and controled by changing the dosage of red mud and vanadium titanium slag, and decorative effect is very superior.
(4) the split-phase furnace transmutation decoration composite material that production obtains can satisfy all service performances of traditional ceramics, i.e., anti-
Tide, partition property and fire resistance, also can satisfy the decorative performance of traditional ceramics, glaze colorant are not used in production process, greatly
Amplitude reduction bring mineral resources, the energy and labor cost due to using glaze colorant are a kind of green, environmental protection production works
Skill.
Detailed description of the invention
Fig. 1 is the microscope figure that obtained split-phase furnace transmutation decoration composite material is produced through embodiment 1.
Fig. 2 is the microscope figure that obtained split-phase furnace transmutation decoration composite material is produced through embodiment 2.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
(1) ingredient: red mud 60%, feldspar 10%, vanadium titanium slag 10%, quartzy 10%, borax is carried out by mass percentage
6%, lepidolite 2 and talcum 2%, are put in Cinker clew furnace, the water quenching, broken and screened after 1450 DEG C of meltings, by quality percentage
Than taking sieve residue to be mixed, wherein 8 mesh~10 mesh, which account for 20%, 11 mesh~15 mesh and account for 60%, 15 mesh~20 mesh, accounts for 20%, i.e.,
For split-phase transmutation raw material；
(2) ingredient: feldspar 47%, clay 27%, flint clay 16%, pyrophyllite 5% and Wen Zu is carried out by mass percentage
Stone 5%, is put in ball mill, ratio of water to material 40:100, and pellet is put in mold, through 200MPa by mist projection granulating after ball milling 36h
Compression moulding obtains green body；
(3) the cloth doses cloth of 7.8 kilograms/square metre will be pressed through split-phase transmutation raw material made from step (1) to through step (2)
On obtained green body, then, firing dry through roller kilns, 1170 DEG C of firing temperature, firing time is 70 minutes, i.e. production is divided
Phase furnace transmutation decoration composite material.
After tested, the water absorption rate of split-phase furnace transmutation decoration composite material is 0.1%, and flexural strength reaches 21MPa.By attached drawing 1
It was found that the split-phase transmutation crystallizing layer of split-phase furnace transmutation decoration composite material is located at green body layer and surface translucent glass layer, split-phase transmutation
The crystal that crystallization is formed is tiny to be evenly distributed, and the decorative effect of metallic luster is presented.
Embodiment 2
(1) carry out ingredient by mass percentage: red mud 50%, feldspar 7%, vanadium titanium slag 20%, quartz 10%, borax 6%,
Lepidolite 5% and talcum 2%, are put in Cinker clew furnace, the water quenching, broken and screened after 1450 DEG C of meltings, by mass percentage
Sieve residue is taken to be mixed, wherein 8 mesh~10 mesh, which account for 20%, 11 mesh~15 mesh and account for 60%, 15 mesh~20 mesh, accounts for 20%, as
Split-phase transmutation raw material；
(2) ingredient: feldspar 47%, clay 27%, flint clay 16%, pyrophyllite 5% and Wen Zu is carried out by mass percentage
Stone 5%, is put in ball mill, ratio of water to material 40:100, and pellet is put in mold, through 200MPa by mist projection granulating after ball milling 36h
Compression moulding obtains green body；
(3) the cloth doses cloth of 4.7 kilograms/square metre will be pressed through split-phase transmutation raw material made from step (1) to through step (2)
On obtained green body, then, firing dry through roller kilns, 1150 DEG C of firing temperature, firing time is 70 minutes, i.e. production is divided
Phase furnace transmutation decoration composite material.
After tested, the water absorption rate of split-phase furnace transmutation decoration composite material is 0.2%, and flexural strength reaches 18MPa.By attached drawing 2
It was found that the split-phase transmutation crystallizing layer of split-phase furnace transmutation decoration composite material is located at green body layer and surface translucent glass layer, split-phase transmutation
The crystal that crystallization is formed is flower-shaped in crystalline substance, and crystalline substance flower shows the decorative effect of metalloid gloss.
Comparative example 1
(1) ingredient: red mud 40%, feldspar 15%, vanadium titanium slag 20%, quartzy 15%, borax is carried out by mass percentage
6%, lepidolite 2% and talcum 2%, are put in Cinker clew furnace, the water quenching, broken and screened after 1450 DEG C of meltings, by quality hundred
Point ratio takes sieve residue to be mixed, wherein and 8 mesh~10 mesh, which account for 20%, 11 mesh~15 mesh and account for 60%, 15 mesh~20 mesh, accounts for 20%,
As split-phase transmutation raw material；
(2) ingredient: feldspar 47%, clay 27%, flint clay 16%, pyrophyllite 5% and Wen Zu is carried out by mass percentage
Stone 5%, is put in ball mill, ratio of water to material 40:100, and pellet is put in mold, through 200MPa by mist projection granulating after ball milling 36h
Compression moulding obtains green body；
(3) the cloth doses cloth of 7.8 kilograms/square metre will be pressed through split-phase transmutation raw material made from step (1) to through step (2)
On obtained green body, then, firing dry through roller kilns, 1170 DEG C of firing temperature, firing time is 70 minutes, i.e. production is divided
Phase furnace transmutation decoration composite material.
It detects and finds through appearance, split-phase furnace transmutation decoration composite material bends, split-phase transmutation crystallizing layer and surface light transmission
Boundary is unintelligible between glassy layer, with the presence of visible bubble between crystallizing layer and green body layer.
Claims (7)
1. a kind of method using red mud through roller kilns production split-phase furnace transmutation decoration composite material, it is characterised in that: specifically include
Following steps:
(1) preparation of split-phase transmutation raw material
Using red mud, feldspar, vanadium titanium slag, quartz, borax, lepidolite and talcum as raw material, it is put in Cinker clew furnace, through 1400-
It is water quenching after 1500 DEG C of meltings, broken and screened, take sieve residue to be mixed, as split-phase transmutation raw material；
(2) preparation of green body
It using feldspar, clay, flint clay, pyrophyllite and Wen Zushi as raw material, is put in ball mill, is made by spraying after ball milling 36h
Grain, pellet is put in mold, repressed molding obtains green body；
(3) preparation of split-phase furnace transmutation decoration composite material
On the green body that will be extremely obtained through step (2) through split-phase transmutation raw material cloth made from step (1), then, burning dry through roller kilns
At i.e. production obtains split-phase furnace transmutation decoration composite material.
2. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: in step (1), being calculated in mass percent, raw material composition is as follows: red mud 50~60%, feldspar 7~10%, vanadium titanium slag
10~20%, quartz 10%, borax 6%, lepidolite 2~5% and talcum 2%.
3. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: step mixes sieve residue described in (1), and by mass percentage, 8 mesh~10 mesh account in sieve residue
20%, 11 mesh~15 mesh account for 60%, and 15 mesh~20 mesh account for 20%.
4. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: in step (2), being calculated in mass percent, raw material composition is as follows: feldspar 47%, clay 27%, flint clay 16%, leaf
Alabaster 5% and Wen Zu stone 5%.
5. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: the ratio of water to material in ball mill described in step (2) is 40:100；The pressure of the compression moulding is 200MPa.
6. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: will on split-phase transmutation raw material cloth to green body, be split-phase transmutation raw material described in step (3) by 4.7~7.8 kilograms/
Square metre cloth doses cloth to green body on.
7. the method according to claim 1 using red mud through roller kilns production split-phase furnace transmutation decoration composite material, special
Sign is: firing described in step (3), and firing temperature is 1150~1170 DEG C, and firing time is 65-75 minutes.
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