CN106242522B - A kind of steel slag base anti-static ceramic and preparation method thereof - Google Patents
A kind of steel slag base anti-static ceramic and preparation method thereof Download PDFInfo
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- CN106242522B CN106242522B CN201610645489.7A CN201610645489A CN106242522B CN 106242522 B CN106242522 B CN 106242522B CN 201610645489 A CN201610645489 A CN 201610645489A CN 106242522 B CN106242522 B CN 106242522B
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- 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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
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Abstract
The present invention discloses a kind of steel slag base anti-static ceramic and preparation method thereof, preparation method comprising steps of A, by include steel slag, clay, aluminium vanadine, stannic oxide formula ball mill is added, add water and ball-milling additive to carry out ball milling；B, the slurry after ball milling carries out sieving processing, is then dusted with spray drying tower, and powder is sent into press compression moulding and obtains adobe after aging；C, adobe feeding dry kiln is dried, after the completion of dry, into roller kiln burning at.One aspect of the present invention realizes that steel slag recycles, and reduces the soil that steel slag accumulation occupies；On the other hand by firing so that harmful element in steel slag is realized solid molten, prevent harmful substance exudation from causing secondary pollution.
Description
Technical field
The present invention relates to field of ceramic preparation more particularly to a kind of steel slag base anti-static ceramic and preparation method thereof.
Background technique
China is the first big country of global steel production, and Chinese output of steel is more than 800,000,000 tons within 2015, Zhan Quanqiu output of steel
49%.In steelmaking process, in order to remove certain unwanted elements in steel, it can will be not required to by the method that slag former is added
The element wanted is precipitated, therefore 1 ton of steel of every production, will generate 150 ~ 200 kilograms of steel slags, and the steel slag that annual China's steel-making generates is super
Cross 100,000,000 tons.Currently, only about 20% steel slag is reused, remaining most of steel slag can only pile up steel mill and nearby wait
Processing, the heavy metal element that the steel slag of bulk deposition not only occupies valuable soil, but also contains in steel slag are easy with rain
Water penetrates into earth's surface and causes secondary pollution.Currently, also have using steel slag as applying filler in cement industry, but because steel slag has
Have high-expansion, therefore the addition steel slag ratio in cement is generally less than 5%, it is therefore desirable to find one kind can high-volume it is low at
This uses the method for steel slag, and this method needs industrialized production easy to accomplish.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of steel slag base anti-static ceramic and its systems
Preparation Method, it is intended to solve the problems, such as that the prior art in high volume low cost can not utilize steel slag.
Technical scheme is as follows:
A kind of preparation method of steel slag base anti-static ceramic, wherein comprising steps of
A, ball mill is added in the formula that steel slag, clay, aluminium vanadine, stannic oxide and former auxiliary agent are constituted, adds water and ball milling
Auxiliary agent carries out ball milling；
B, the slurry after ball milling carries out sieving processing, is then dusted with spray drying tower, and powder is sent after aging
Enter press compression moulding and obtains adobe；
C, adobe feeding dry kiln is dried, after the completion of dry, into roller kiln burning at.
The preparation method of the steel slag base anti-static ceramic, wherein further include potassium feldspar in the formula.
The preparation method of the steel slag base anti-static ceramic, wherein the mass ratio of steel slag in formula is 30% ~ 60%,
The mass ratio of clay in formula is 20% ~ 40%, and the mass ratio of aluminium vanadine in formula is 20% ~ 45%, and stannic oxide is being formulated
In mass ratio be 3% ~ 8%, the mass ratio of potassium feldspar in formula be 3% ~ 10%.
The preparation method of the steel slag base anti-static ceramic, wherein by mass percentage, in the steel slag, oxidation
Iron content is 8% ~ 12%, and calcium oxide content is 8% ~ 14%, and stannic oxide content is 3% ~ 8%, and alumina content is 25% ~ 35%, two
Silica content is 25% ~ 45%.
The preparation method of the steel slag base anti-static ceramic, wherein in the step A, the control of ball milling fineness is as follows: no
1.0% can be less than or equal to by the mass ratio of 250 meshes.
The preparation method of the steel slag base anti-static ceramic, wherein in the step B, slurry is only sieved with 100 mesh sieve, no
Handled except iron.
The preparation method of the steel slag base anti-static ceramic, wherein in the step B, using dry-pressing formed method
Molding.
The preparation method of the steel slag base anti-static ceramic, wherein in the step C, adobe is after drying, in brick
Base surface carries out pattern decorative.
The preparation method of the steel slag base anti-static ceramic, wherein in the step C, burnt using reducing atmosphere
At firing temperature is 1180 degree ~ 1220 degree.
A kind of steel slag base anti-static ceramic, wherein be prepared using preparation method as described above.
The utility model has the advantages that the present invention has little using the iron oxide in steel slag after firing in Ceramic Tiles
Characteristic (effect for not having antistatic) and the high feature of steel slag internal oxidition content of magnesium are mentioned significantly by adding a small amount of stannic oxide
The electric conductivity of high ceramics, so that having the function of antistatic by the Ceramic Tiles of primary raw material of steel slag.Meanwhile the nocuousness in steel slag
Element other ingredients in sintering process and in green body are melted together admittedly, and harmful element is effectively prevent to ooze out.One aspect of the present invention
It realizes that steel slag recycles, reduces the soil that steel slag accumulation occupies；On the other hand by firing so that the harmful element in steel slag is real
It now melts admittedly, prevents harmful substance exudation from causing secondary pollution.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of steel slag base anti-static ceramic of the present invention.
Specific embodiment
The present invention provides a kind of steel slag base anti-static ceramic and preparation method thereof, to make the purpose of the present invention, technical solution
And effect is clearer, clear, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
Since the main component of steel slag is silica, iron oxide, calcium oxide and magnesia, wherein silica, oxidation
Calcium and magnesia are chemical components needed for architectural pottery product, therefore steel slag has the potentiality used as ceramic raw material；Oxidation
Iron is also one of main component of steel slag, and the characteristic that iron oxide has forbidden band narrow, the forbidden bandwidth of iron oxide only has 2.3eV, iron
The outer-shell electron of the ion conduction band easy to accomplish that transits to realizes conduction, therefore iron oxide content height makes steel slag have one in steel slag
Fixed conductive capability, but formability and firing range in view of ceramic blank are needed in actual production, therefore in ceramics
The usage amount of steel slag has certain restrictions in formula, therefore iron oxide contained by steel slag is only leaned on to be not enough to that steel slag base Ceramic Tiles is allowed to have
There is the effect of antistatic.
The present invention enhances the conductive capability of steel slag Ceramic Tiles by addition conductive oxide in formula, so that green body
Resistivity meets the standard of antistatic after firing.According to the high characteristic of content of magnesia in steel slag and magnesium ion radius and tin ion
The close feature of radius, selects stannic oxide as the conductive oxide for improving steel slag ceramic tile electric conductivity, and steel slag ceramic tile is being burnt into
Magnesium ion enters in the lattice of stannic oxide in the magnesia in steel slag in the process, is doped to stannic oxide, improves dioxy
The conductive capability for changing tin can achieve the resistance that steel slag base ceramics can be greatly lowered in a small amount of addition conductive oxide in this way
Rate.Therefore, the present invention is primary raw material using steel slag, clay and bauxite, adds a small amount of stannic oxide and makes one kind with anti-
The ceramic product of electrostatic function.
Referring to Fig. 1, Fig. 1 is a kind of process of the preparation method preferred embodiment of steel slag base anti-static ceramic of the present invention
Figure, as shown, itself comprising steps of
S1, ball mill is added in the formula that steel slag, clay, aluminium vanadine, stannic oxide and former auxiliary agent are constituted, adds water and ball milling
Auxiliary agent carries out ball milling；
Slurry after S2, ball milling carries out sieving processing, is then dusted with spray drying tower, powder after aging,
It is sent into press compression moulding and obtains adobe；
S3, adobe feeding dry kiln is dried, after the completion of dry, into roller kiln burning at.
Wherein, it is not enough to that steel slag base ceramics is allowed to have the effect of antistatic for iron oxide electric conductivity in steel slag, utilizes steel
The high feature of content of magnesia by adding a small amount of stannic oxide in formula in slag, the magnesia in sintering process in steel slag
Stannic oxide is doped, realizes that adding a small amount of stannic oxide can just make steel slag base ceramics have the effect of antistatic.This
The invention feature high using iron oxide in steel slag and content of magnesia, is realized based on steel slag by adding a small amount of stannic oxide
Ceramic Tiles have the function of antistatic, expand the use scope of steel slag, improve the utility value of steel slag.
It specifically, in step sl, further include potassium feldspar in the formula.The mass ratio of steel slag in formula be 30% ~
60%, the mass ratio of clay in formula is 20% ~ 40%, and the mass ratio of aluminium vanadine in formula is 20% ~ 45%, and stannic oxide exists
Mass ratio in formula is 3% ~ 8%, and the mass ratio of potassium feldspar in formula is 3% ~ 10%.Preferably, the matter of steel slag in formula
Amount is than being 40% ~ 60%.
In step sl, by mass percentage, in the steel slag, iron oxide content is 8% ~ 12%, and calcium oxide content is
8% ~ 14%, stannic oxide content is 3% ~ 8%, and alumina content is 25% ~ 35%, and dioxide-containing silica is 25% ~ 45%.Wherein aoxidize
Aluminium content is up to 25% ~ 35%, and the firing range of body recipe can be improved.
In the step S1, the control of ball milling fineness is as follows: cannot be less than or equal to by the mass ratio of 250 meshes
1.0%.After ball milling, each material will mix more evenly.
Further, in the step S2, slurry is only sieved with 100 mesh sieve, without handling except iron.Not except iron reduces process,
It can guarantee that there are the oxides such as enough stannic oxides in formula simultaneously.
Further, it in the step S2, is formed using dry-pressing formed method.Dry-pressing formed mode can will be of the invention
In green body suppress more evenly, and improve compacting efficiency.
Further, in the step S3, adobe carries out pattern decorative after drying, on adobe surface, and wherein pattern fills
There is anti-static effect after decorations glaze firing used.
Further, it in the step S3, is burnt into using reducing atmosphere (such as weakly reducing atmosphere), firing temperature 1180
~ 1220 degree of degree.
Further, in the step S3, when firing, uses water-gas for fuel.In the case where the air amount of blasting is constant,
The water-gas amount of blasting can increase by 5% ~ 15%(volume).
The present invention also provides a kind of steel slag base anti-static ceramics, and preparation method as described above is used to be prepared.
Embodiment one:
Step 1: adding prescription quality using 50% steel slag, 27% clay, 20% bauxite and 3% stannic oxide as composition of raw materials
Water than 60% and 1.5% ball-milling additive carry out ball milling, and slurry fineness is milled to 0.9%, cannot pass through the quality of 250 meshes
Ratio characterization；
Step 2: the slurry after qualified to fineness confirmation sieves with 100 mesh sieve, then spray drying powder processed is carried out, then uses press
It carries out dry-pressing formed obtaining adobe；
Step 3: adobe enters dry kiln and is dried after molding, roller kilns are entered by pipeline after dry and are burnt
At firing temperature is 1210 degree, and firing atmosphere is reducing atmosphere (such as weakly reducing atmosphere, similarly hereinafter)；
In the present embodiment, the ratio of steel slag is 50% in formula, the ratio 27% of clay, the ratio of bauxite are 20%, outside
Adding ratio is 3% stannic oxide, by ball milling, be sieved, dust and suppress after, then be dried, finally enter roller kilns,
It is burnt at a temperature of 1210 degree.For Ceramic Tiles in the present embodiment after 1210 degree of firings, mean water absorption rate is 15.3%, is broken
It splits modulus and reaches 25MPa；It is 5 × 10 with the resistance that ZC25-4 type insulation resistance meter measures ceramic body7, meet static-electricity proof tile
Required resistivity is 105~109Requirement.
Embodiment two:
Step 1: adding prescription quality using 40% steel slag, 25% clay, 30% bauxite and 5% stannic oxide as composition of raw materials
Water than 60% and 1.5% ball-milling additive carry out ball milling, and slurry fineness is milled to 0.9%, cannot pass through the ratio of 250 meshes
Characterization；
Step 2: the slurry of fineness confirmation qualification is sieved with 100 mesh sieve, then spray drying powder processed is carried out, then uses press
It carries out dry-pressing formed obtaining adobe；
Step 3: adobe enters dry kiln and is dried after molding, after the completion of dry, then by pipeline adobe is sent into
Roller kilns 1220 at a temperature of be burnt into, firing atmosphere is reducing atmosphere；
In the present embodiment, the additional proportion of steel slag is 40% in formula, and the additional proportion of clay is 25%, and bauxite adds
Entering ratio is 30%, and additional ratio is 5% stannic oxide, by ball milling, be sieved, dust and suppress after, then be dried, it is most laggard
Enter roller kilns, 1220 degree at a temperature of be burnt into.Ceramic Tiles in the present embodiment are after 1220 degree of firings, the water suction of ceramic tile
Rate is 14.7%, and the modulus of rupture reaches 30MPa；The point-to-point resistance in brick face is 8 × 107, reach national antistatic national standard
(105~109) requirement.
Embodiment three:
Step 1: adding using 40% steel slag, 30% clay, 20% bauxite, 5% potassium feldspar and 5% stannic oxide as composition of raw materials
Water of the prescription quality than 60% and 1.5% ball-milling additive is added to carry out ball milling, slurry fineness is milled to 1.0%, cannot pass through 250
The ratio of mesh characterizes；
Step 2: the slurry of fineness confirmation qualification is sieved with 100 mesh sieve, then spray drying powder processed is carried out, then uses press
It is pressed；
Step 3: green body enters dry kiln and is dried after molding, green body is after drying, then by pipeline by adobe
Inlet roller conveyor kiln 1220 at a temperature of be burnt into；
In the present embodiment, the additional proportion of steel slag is 40% in formula, and the additional proportion of clay is 30%, and bauxite adds
Entering ratio is 20%, and the additional proportion of potassium feldspar is 5%, and the additional proportion of stannic oxide is 5%, by ball milling, be sieved, dust and
After compacting, then be dried, finally enter roller kilns, 1220 degree at a temperature of be burnt into.Ceramic Tiles in the present embodiment are passed through
After 1220 degree of firings, the water absorption rate of ceramic tile is 15.6% after firing, and the modulus of rupture reaches 28MPa；The point-to-point resistance in brick face is 6
×107, reach national antistatic national standard (105~109) requirement.
Example IV:
Wherein, the first step, the operation of second step are consistent with the operation of the middle first step of embodiment two and second step；
Step 3: adobe enters dry kiln and is dried after molding, then adobe is carried out with mill blank machine to polish processing, so
Afterwards brick face apply can antistatic overglaze, carry out pattern decorative with ink-jet printer, finally again adobe surface apply have prevent it is quiet
The throwing glaze of electric effect, finally by pipeline by adobe Inlet roller conveyor kiln 1220 at a temperature of be burnt into；
In the present embodiment, the additional proportion of steel slag is 40% in body recipe, and the additional proportion of clay is 25%, bauxite
Additional proportion be 30%, additional ratio is 5% stannic oxide, by ball milling, is sieved, dusts and compression moulding, after drying
Apply overglaze with anti-static effect in glaze line and throw glaze, carry out pattern decorative with inkjet printing, used in antistatic face
The point-to-point resistivity 3 × 10 of glaze7, used in antistatic throw glaze point-to-point resistivity 5 × 108, press done
After molded, after dry kiln is dried, roller kilns be sent by pipeline and are burnt into, wherein firing temperature is 1220
Degree, the water absorption rate of ceramic tile is 14.3% after firing, and the modulus of rupture reaches 35MPa；The point-to-point resistance in brick face is 3 × 107, reach
To national antistatic national standard (105~109) requirement.
In conclusion main several improvement of the invention are:
1), the feature high using residual oxygen iron content in steel slag, using iron oxide as green body conductive compositions, by adding
Add a small amount of stannic oxide to reduce the resistivity of Ceramic Tiles, makes the function for having antistatic using the Ceramic Tiles of steel slag primary raw material
Energy；
2), the characteristic high using content of magnesia in steel slag, adds stannic oxide in formula, utilizes in sintering process
Magnesia in steel slag is doped stannic oxide, enhances the conductive capability of stannic oxide, realizes and adds a small amount of stannic oxide
The effect of the resistivity of steel slag Ceramic Tiles can be greatly lowered；
3), by addition bauxite and clay, the content of the aluminium oxide in body recipe is on the one hand improved, green body is widened
The firing range of formula, on the other hand the plasticity of formula, reduces blank forming difficulty.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (7)
1. a kind of preparation method of steel slag base anti-static ceramic, which is characterized in that comprising steps of
A, it will include the formula addition ball mill of steel slag, clay, aluminium vanadine, stannic oxide and potassium feldspar, add water and ball-milling additive
Carry out ball milling；
B, the slurry after ball milling carries out sieving processing, is then dusted with spray drying tower, and powder is sent into pressure after aging
Machine compression moulding obtains adobe；
C, adobe feeding dry kiln is dried, after the completion of dry, into roller kiln burning at；
The mass percent of steel slag in formula is 30% ~ 60%, and the mass percent of clay in formula is 20% ~ 40%, aluminium vanadium
The mass percent of soil in formula is 20% ~ 45%, and the mass percent of stannic oxide in formula is 3% ~ 8%, and potassium feldspar exists
Mass percent in formula is 3% ~ 10%, and the sum of mass percent of the above components is 100%；
By mass percentage, in the steel slag, iron oxide content is 8% ~ 12%, and calcium oxide content is 8% ~ 14%, stannic oxide
Content is 3% ~ 8%, and alumina content is 25% ~ 35%, and dioxide-containing silica is 25% ~ 45%, and the sum of the above components content is
100%；
Realizing the ceramics based on steel slag by a small amount of stannic oxide of addition has the function of antistatic.
2. the preparation method of steel slag base anti-static ceramic according to claim 1, which is characterized in that in the step A, ball
Grinding rate control is as follows: cannot be less than or equal to 1.0% by the mass ratio of 250 meshes.
3. the preparation method of steel slag base anti-static ceramic according to claim 1, which is characterized in that in the step B, slurry
Material only sieves with 100 mesh sieve, without handling except iron.
4. the preparation method of steel slag base anti-static ceramic according to claim 1, which is characterized in that in the step B, adopt
It is formed with dry-pressing formed method.
5. the preparation method of steel slag base anti-static ceramic according to claim 1, which is characterized in that in the step C, brick
Base carries out pattern decorative after drying, on adobe surface.
6. the preparation method of steel slag base anti-static ceramic according to claim 1, which is characterized in that in the step C, adopt
It is burnt into reducing atmosphere, firing temperature is 1180 degree ~ 1220 degree.
7. a kind of steel slag base anti-static ceramic, which is characterized in that use preparation method system as claimed in any one of claims 1 to 6
It is standby to form.
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Effective date of registration: 20190703 Address after: 543000 Zhonghe Ceramic Industrial Park C District, Tandong Village, Tengzhou Town, Wuzhou City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi European Sano Ceramics Co., Ltd. Address before: 528138 fan Lake Industrial Park, Leping Town, Sanshui District, Foshan, Guangdong Patentee before: Foshan Oushennuo Ceramic Co., Ltd. |