CN106977176A - A kind of method of utilization high-calcium fly ass low-temperature sintering ceramic brick - Google Patents
A kind of method of utilization high-calcium fly ass low-temperature sintering ceramic brick Download PDFInfo
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- CN106977176A CN106977176A CN201610031115.6A CN201610031115A CN106977176A CN 106977176 A CN106977176 A CN 106977176A CN 201610031115 A CN201610031115 A CN 201610031115A CN 106977176 A CN106977176 A CN 106977176A
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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
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- 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
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- 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
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- 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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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
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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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
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Abstract
The invention discloses a kind of method that utilization flyash fires standby Ceramic Tiles, comprise the following steps：1) the water soluble alkali solution system that high-calcium fly ass is added into 40-150g/L reacts；2) by step 1) in the filtering of reacted slurries, washing, obtained filter residue is the modified high-calcium fly ass in surface；3) by the modified high-calcium fly ass in surface with clay, flux class feed proportioning is levigate；4) granulate；5) by step 4) in spherical powder be molded in a mold, dry after obtain Ceramic Tiles green compact；6) by step 5) in obtained Ceramic Tiles green compact Ceramic Tiles are made through heating, insulation and cooling.The present invention prepares the characteristics of gained Ceramic Tiles have easy fired.
Description
Technical field
The invention belongs to industrial solid castoff comprehensive utilization and novel building ceramic material invention field, and in particular to
Comprehensively utilize the new method of industrial solid castoff high-calcium fly ass.
Background technology
Flyash be large-size thermal power plant it is coal-fired after a kind of solid waste for discharging, it is maximum single that it has turned into China
One solid pollution source.
High-calcium fly ass is that a kind of calcium oxide given off when thermal power plant uses lignite, ub-bituminous coal as fuel contains
The higher flyash of amount.In recent years, developing rapidly with power industry, increasing Generator Set has been thrown
Enter operation, more lignite, ub-bituminous coals with high volatile are used as power fuel.In certain areas, high-calcium powder
The discharge capacity of coal ash considerably beyond Class F fly ash, forces people that notice is more put into high-calcium fly ass
Exploitation in.
In recent years, real estate industry of China fast development, it is new that day also occurs for ceramic tile production industry related to this
Month different change.However as increasing substantially for Ceramic Tiles yield, in ceramic tile production used clay class raw material and
Flux class raw material is also increasingly deficient.Ceramic tile production industry raw material imbalance between supply and demand becomes increasingly conspicuous.
The chemical composition of high-calcium fly ass and thing phase composition are close with Ceramic Tiles raw material, for this high-calcium fly ass profit
With deficiency, how the problem of ceramic tile production raw material resources are in short supply uses high-calcium fly ass in ceramic tile production
Through as people's question of common concern.
High-calcium fly ass has the characteristics of fine size, vitreum content are high, fusing point is low, reactivity is high, utilizes its work
Can be with low-temperature sintering ceramic product during for raw material.But high calcium ash is utilized with being a kind of poor material ordinary fly ash
The problem of its plasticity is poor must be solved when it is as Production of Ceramics raw material.Chinese patent application CN2015104390434
A kind of preparation method of fly ash base Imitation Rock Porcelain Tiles is disclosed, the plasticity of flyash is improved by Alkaline pretreatment, is solved
Fly ash base Ceramic Tiles of having determined will dry qualification rate from 85% the problem of blank strength is low in process of production, successfully
Lifted to more than 99%.But, production cost high the problem of high there are still firing temperature.
The content of the invention
It is an object of the invention to provide it is a kind of to the colms such as thermal power plant combusting brown coal or ub-bituminous coal produce
High-calcium fly ass carries out the method for surface modification, so as to increase its plasticity, and utilizes modified high-calcium fly ass
As raw materials for production, novel building ceramic material is prepared by easy fired.
The method that the utilization high-calcium fly ass easy fired that the present invention is provided prepares environmentally friendly ecological ceramic brick includes
Following steps：
1) high-calcium fly ass is added to 40-150g/L water soluble alkali solution system, reaction temperature is 50-200 DEG C,
Liquid-solid ratio is 2-8, and the reaction time is 0.5-2h；
2) by step 1) in the filtering of reacted slurries, washing, obtained filter residue is the modified high-calcium powder in surface
Coal ash；
3) by the modified high-calcium fly ass in surface and clay, flux class feed proportioning, adding water to be mixed and finely ground obtains wet
Slurries after mill, or the dry grinding that do not add water；
4) by step 3) in slurries after wet-milling dry and granulate spherical powder for aqueous 5-10%, or will step
It is rapid 3) in dry grind after obtained powder add water and granulate as aqueous 5-10% spherical powder, foregoing spherical powder is entered
Feed bin is old with standby；
5) by step 4) in spherical powder be molded in a mold, dry after obtain Ceramic Tiles green compact；
6) by step 5) in obtained Ceramic Tiles green compact Ceramic Tiles are made through heating, insulation and cooling.
It is preferred that, CaO content is more than 5wt% in the high-calcium fly ass.
It is preferred that, the water soluble alkali is potassium hydroxide or sodium hydroxide.
It is preferred that, the step 3) in dispensing wet-milling to particle diameter is less than 20 mesh or dispensing dry grinds to less than 20
Mesh.
It is preferred that, step 1) water soluble alkali solution is used for NaOH solution or KOH solution.
It is preferred that, step 3) in raw material to include the modified high-calcium fly ass 20-90wt% in surface, clay class former
Expect 10-50wt%, flux class raw material 10-50wt%.
It is preferred that, step 6) in, firing range when firing pottery brick is 900-1100 DEG C, fires Imitation Rock Porcelain Tiles
When firing range be 1000-1200 DEG C, programming rate be 100-1000 DEG C/h, sintering process maximum temperature
Soaking time is 0.1-3h.
It is preferred that, the flux class raw material includes feldspar raw material, talcum, carbonate raw material, wollastonite raw material, firefly
One or more in stone, borax and boric acid.
It is preferred that, step 5) described in briquetting pressure be 20-80MPa.
The present invention has following beneficial effect：
1st, the plasticity that preconditioning technique improves high-calcium fly ass is modified by surface, solves high-calcium fly ass base
Ceramic Tiles improve green compact qualification rate the problem of green strength is low in process of production, to pottery when meeting large-scale production
The requirement of green compact of ceramic tile intensity.
2nd, the high value added utilization of high-calcium fly ass is realized, the addition content of high-calcium fly ass is solved up to 90%
The problem of a large amount of high-calcium fly asses accumulation pollution environment, at the same be also clay class raw material in short supply in ceramic tile production and
Feldspar raw material have found alternate resources, with important economical, social and environment protection significance.
3rd, the firing temperature that the present invention is used is low, belongs to easy fired technique, ceramic tile production mistake can be saved on a large scale
Energy consumption in journey, reduces production cost, economical advantage.
4th, the present invention prepare gained pottery brick water absorption rate between 10-20%, rupture strength be much larger than 15MPa,
Linear shrinkage ratio is less than 1.2%, meets GB/T4100-2015 quality requirements.
5th, the present invention prepares gained Imitation Rock Porcelain Tiles water absorption rate and is much larger than 35MPa, linear shrinkage ratio less than 0.5%, rupture strength
Less than 20%, meet GB/T4100-2015 quality requirements.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Embodiment
With the drawings and specific embodiments, the present invention is further detailed explanation below.
Embodiment 1
This example uses In Xilingol League In Inner Mongolia thermal power plant high-calcium fly ass, and its main component is 42.25%
SiO2, 14.94% Al2O3, 5.35% CaO and 10.11% Fe2O3.High-calcium fly ass base is environment-friendly
The production of type ecology pottery brick is according to Fig. 1 technological process.The surface for carrying out high-calcium fly ass first is modified pretreatment,
High-calcium fly ass is added to 80g/L NaOH solution system, reaction temperature is 90 DEG C, and liquid-solid ratio is 4, instead
It is 1h between seasonable.Slurries are filtered, washed, obtain the modified high-calcium fly ass in surface and bentonite, talcum,
Diopside, powdered whiting carry out dispensing according to 50%, 25%, 20%, 4%, 1% ratio, add 35% (ball
Grind the water and 0.3% sodium tripolyphosphate (the 0.3% of siccative quality) 35%) of rear slurry gross mass, being milled to
For homogeneous slurry (ball milling rear slurry screen over-size after 250 mesh sieves is approximately equal to 1%).It is by slurries drying to moisture content
8% spherical powder, and spherical powder all passes through 50 mesh sieves.Old 24h aftershapings, briquetting pressure is 30MPa,
Dried after shaping and (dry qualification rate 99.5%, the anti-folding 6.03MPa of base substrate meets daily production needs).After drying
Burn till, firing temperature is 1100 DEG C, is incubated 10min.Ceramic brick product is obtained after cooling, its water absorption rate be 15.90%,
Rupture strength is 26.40MPa, and linear shrinkage ratio is 0.9%, meets GB/T4100-2015 quality requirements.
Embodiment 2
This example uses In Xilingol League In Inner Mongolia thermal power plant high-calcium fly ass, and its main component is 51.45%
SiO2, 22.30% Al2O3, 6.63% CaO and 4.47% Fe2O3.High-calcium fly ass base is environment-friendly
The production of type ecology pottery brick is according to Fig. 1 technological process.The surface for carrying out high-calcium fly ass first is modified pretreatment,
High-calcium fly ass is added to 90g/L NaOH solution system, reaction temperature is 100 DEG C, and liquid-solid ratio is 6, instead
It is 2h between seasonable.Slurries are filtered, washed, obtain the modified high-calcium fly ass in surface and pyrophillite, diopside,
Bentonite, powdered whiting carry out dispensing according to 40%, 20%, 24%, 15%, 1% ratio, add 48%
The water and 0.8% sodium metasilicate (the 0.8% of siccative quality) of (the 48% of ball milling rear slurry gross mass), being milled to
For homogeneous slurry (ball milling rear slurry screen over-size after 250 mesh sieves is approximately equal to 1%).It is by slurries drying to moisture content
10% spherical powder, and spherical powder all passes through 50 mesh sieves.Old 2h aftershapings, briquetting pressure is 25MPa,
Dried after shaping and (dry qualification rate 99.6%, the anti-folding 5.85MPa of base substrate meets daily production needs).After drying
Burn till, firing temperature is 900 DEG C, is incubated 60min.Ceramic brick product is obtained after cooling, its water absorption rate be 16.85%,
Rupture strength is 23.50MPa, and linear shrinkage ratio is 0.9%, meets GB/T4100-2015 quality requirements.
Embodiment 3
This example uses In Xilingol League In Inner Mongolia thermal power plant high-calcium fly ass, and its main component is 55.57%
SiO2, 21.47% Al2O3, 5.12% CaO and 6.80% Fe2O3.High-calcium fly ass base is environment-friendly
The production of type ecology pottery brick is according to Fig. 1 technological process.The surface for carrying out high-calcium fly ass first is modified pretreatment,
High-calcium fly ass is added to 150g/L NaOH solution system, reaction temperature is 80 DEG C, and liquid-solid ratio is 3, instead
It is 0.5h between seasonable.Slurries are filtered, washed, the modified high-calcium fly ass in surface is obtained and kaolin, potassium is long
Stone, pyrophillite carry out dispensing according to 40%, 23%, 20%, 17% ratio, and adding 40%, (ball milling rear slurry is total
The water and 1% sodium humate (the 1% of siccative quality) 40%) of quality, are milled to and turn to homogeneous slurry (ball milling
1%) rear slurry screen over-size after 250 mesh sieves is approximately equal to.By the spherical powder that slurries drying to moisture content is 7%, and
And spherical powder all passes through 50 mesh sieves.Old 12h aftershapings, briquetting pressure is 35MPa, is dried after shaping
(drying qualification rate 99.1%, the anti-folding 6.00MPa of base substrate meets daily production needs).Burn till, burn till after drying
Temperature is 1020 DEG C, is incubated 25min.Porcelain brick product is obtained after cooling, its water absorption rate is 0.14%, rupture strength
For 45.80MPa, linear shrinkage ratio is 12.09%, meets GB/T4100-2015 quality requirements.
Embodiment 4
This example uses In Xilingol League In Inner Mongolia thermal power plant high-calcium fly ass, and its main component is 42.25%
SiO2, 14.94% Al2O3, 5.35% CaO and 10.11% Fe2O3.High-calcium fly ass base is environment-friendly
The production of type ecology pottery brick is according to Fig. 1 technological process.The surface for carrying out high-calcium fly ass first is modified pretreatment,
High-calcium fly ass is added to 120g/L NaOH solution system, reaction temperature is 200 DEG C, and liquid-solid ratio is 5,
Reaction time is 1.5h.Slurries are filtered, washed, the modified high-calcium fly ass in surface and bentonite, cunning is obtained
Stone, diopside, powdered whiting carry out dispensing according to 50%, 25%, 20%, 1%, 4% ratio, and mixing is dry
Grind to possess the dry mash that a deciding grade and level is matched somebody with somebody (powder screen over-size after 250 mesh sieves is approximately equal to 1% after ball milling).By dry powder
Add water the spherical powder that granulation is aqueous 6%, and spherical powder all passes through 50 mesh sieves.Old 1h aftershapings,
Briquetting pressure is 50MPa, is dried after shaping and (dries qualification rate 99.3%, the anti-folding 5.95MPa of base substrate meets daily
Production needs).Burnt till after drying, firing temperature is 980 DEG C, is incubated 30min.Ceramic brick product is obtained after cooling,
Its water absorption rate is that 17.50%, rupture strength is 19.95MPa, and linear shrinkage ratio is 0.9%, meets GB/T4100-2015
Quality requirement.
Embodiment 5
This example uses Shandong Dezhou thermal power plant high-calcium fly ass, and its main component is 53.06% SiO2、
22.05% Al2O3, 9.76% CaO and 7.78% Fe2O3.The environmentally friendly ecological pottery of high-calcium fly ass base
The production of matter brick is according to Fig. 1 technological process.The surface for carrying out high-calcium fly ass first is modified pretreatment, by high calcium
Flyash is added to 100g/L NaOH solution system, and reaction temperature is 95 DEG C, and liquid-solid ratio is 7, the reaction time
For 50min.Slurries are filtered, washed, the modified high-calcium fly ass in surface and kaolin, potassium feldspar, leaf is obtained
Cured stone carries out dispensing according to 40%, 20%, 20%, 20% ratio, and mixing dry grinding is to possess the dry powder that a deciding grade and level is matched somebody with somebody
Expect (powder screen over-size after 250 mesh sieves is approximately equal to 1% after ball milling).By dry powder add water granulation for aqueous 8% it is spherical
Powder, and spherical powder all passes through 50 mesh sieves.Old 36h aftershapings, briquetting pressure is 40MPa, shaping
Dry afterwards and (dry qualification rate 99.5%, the anti-folding 6.55MPa of base substrate meets daily production needs).Burnt till after drying,
Firing temperature is 1150 DEG C, is incubated 15min.Ceramic brick product is obtained after cooling, its water absorption rate is 0.05%, anti-folding
Intensity is 50.40MPa, and linear shrinkage ratio is 13.65%, meets GB/T4100-2015 quality requirements.
It should be noted last that, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover
Among scope of the presently claimed invention.
Claims (7)
1. a kind of method that utilization flyash fires standby Ceramic Tiles, methods described comprises the following steps：
1) high-calcium fly ass is added to 40-150g/L water soluble alkali solution system, reaction temperature is 50-200 DEG C,
Liquid-solid ratio is 2-8, and the reaction time is 0.5-2h；
2) by step 1) in the filtering of reacted slurries, washing, obtained filter residue is the modified high-calcium powder in surface
Coal ash；
3) by the modified high-calcium fly ass in surface and clay, flux class feed proportioning, adding water to be mixed and finely ground obtains wet
Slurries after mill, or the dry grinding that do not add water；
4) by step 3) in slurries after wet-milling dry and granulate as aqueous 5-10% and possess the ball of certain particle size
Shape powder, or by step 3) in dry grind after obtained powder add water and granulate as aqueous 5-10% and possess certain
The spherical powder of granularity, foregoing spherical powder pan feeding storehouse is old with standby；
5) by step 4) in spherical powder be molded in a mold, dry after obtain Ceramic Tiles green compact；
6) by step 5) in obtained Ceramic Tiles green compact Ceramic Tiles are made through heating, insulation and cooling.
2. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that step 1)
Used aqueous slkali is NaOH or KOH solution.
3. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that step 3)
In raw material proportioning be：The modified high-calcium fly ass 20-90wt% in surface, clay class raw material 10-50wt%, flux
Class raw material 10-50wt%.
4. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that step 6)
In, firing range when firing pottery brick is 900-1100 DEG C, and firing range when firing Imitation Rock Porcelain Tiles is
1000-1200 DEG C, programming rate is 100-1000 DEG C/h, and the soaking time of sintering process maximum temperature is 0.1-3h.
5. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that the flux class is former
Material include feldspar raw material, talcum, carbonate raw material, wollastonite raw material, fluorite, borax and one kind in boric acid or
It is a variety of.
6. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that step 4)
In obtained spherical powder particles be less than 20 mesh.
7. the method for flyash firing ceramics brick is utilized according to claim 1, it is characterised in that step 5)
Briquetting pressure is 20-80MPa.
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| CN201610031115.6A CN106977176A (en) | 2016-01-18 | 2016-01-18 | A kind of method of utilization high-calcium fly ass low-temperature sintering ceramic brick |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857250A (en) * | 2018-08-22 | 2020-03-03 | 中国科学院过程工程研究所 | Method for preparing ceramic tile by using fly ash as raw material |
| JP2022504880A (en) * | 2018-10-15 | 2022-01-13 | ベコー アイピー ホールディングス リミテッド | Ceramic particle mixture containing coal-burning fly ash |
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|---|---|---|---|---|
| CN1249281A (en) * | 1999-08-11 | 2000-04-05 | 孙救来 | Process for modifying and applying fly ash |
| CN103553568A (en) * | 2013-10-12 | 2014-02-05 | 中国神华能源股份有限公司 | Porcelain tile and preparation method thereof, and purpose of residue of aluminium extraction from fly ash |
| CN105174909A (en) * | 2015-08-05 | 2015-12-23 | 澧县新鹏陶瓷有限公司 | Ceramic product using fly ash as main raw material and preparation method thereof |
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2016
- 2016-01-18 CN CN201610031115.6A patent/CN106977176A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110857250A (en) * | 2018-08-22 | 2020-03-03 | 中国科学院过程工程研究所 | Method for preparing ceramic tile by using fly ash as raw material |
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| JP7506933B2 (en) | 2018-10-15 | 2024-06-27 | ベコー アイピー ホールディングス リミテッド | Ceramic particle mixtures containing coal combustion fly ash. |
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