CN101928135A - Calcium hexaluminate lightweight refractory brick and preparation method thereof - Google Patents
Calcium hexaluminate lightweight refractory brick and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a calcium hexaluminate lightweight refractory brick, in particular to a high-quality refractory material with low heat conduction coefficient, good stability under high-temperature reducing atmosphere, good alkali resistance and slag erosion resistance and long service life for a high-temperature kiln lining, and belongs to the technical field of refractory materials. Calcium hexaluminate is used as a main crystal phase, and the sum of the main chemical components Al2O3 and CaO of the calcium hexaluminate is more than 90 weight percent. Calcium carbonate, calcium hydroxide, calcium oxide, limestone or lime or the like is used as a calcium source; and aluminum oxide, aluminum hydroxide or the like is used as an aluminum source. The calcium hexaluminate lightweight refractory brick is prepared by a series processes of mixing the materials uniformly according to the theory of the calcium hexaluminate, grinding the mixture, adding a certain amount of pore forming agent into the mixture and stirring the mixture uniformly, then performing half dry vibration casting, wet adjusting controllable drying, high-temperature air introducing pore formation, one-step reductive reaction sintering, cutting and processing and the like. The lightweight refractory brick for the high-temperature kiln lining has low heat conduction coefficient and long service life, and can provide efficient and energy-saving guarantee for industrial furnace equipment.
Description
Technical field:
The present invention relates to a kind of calcium hexaluminate lightweight refractory brick and preparation method thereof, belong to fire resisting material field.
Background technology:
China's Economic development is rapid, and the development of Energy production relatively lags behind manyly.It is energy-conservation solving another way of energy starved, promptly reduces the utilising efficiency of thermosteresis, raising heat energy, reduces energy dissipation.In the world energy conservation project is considered as " the 5th energy ", its meaning is very important.Therefore, greatly develop thermal insulation material industry, extensively adopt the high-quality thermal insulation material, health, the steady progression of China's economic construction had important practical significance.
The Industrial Stoves furnace lining generally accounts for 20～45% of Industrial Stoves total energy consumption with the accumulation of heat and the heat lost by radiation of thermal insulation material.Common pure aluminium silicate light weight refractory brick, high alumina light weight refractory brick, alumina hollow ball refractory brick and refractory fibre product are traditional industrial kiln lightweight refractories.Former three exists that density is higher, thermal conductivity is higher, heat storage capacity is big, anti-thermal shock less stable, work-ing life are short, problem such as energy-saving effect difference in the use.Though refractory fibre product is being confirmed aspect the energy-saving effect of kiln fully, limits the outstanding problem that it continues development but still exist, as: the very low effect that can't bear support structure of intensity; Use temperature easy efflorescence and fall slag more than 1200 ℃ the time, and the erosive wear performance of high temperature resistance Dual-Phrase Distribution of Gas olid (high-temperature flue gas and high-temperature flue gas/solid combustion particle) is relatively poor, not only work-ing life shorter, also have a strong impact on the surface quality of Low fire ceramic product " it is dirty to fall " defective; In production and use, there is carcinogenic risk (European Union has classified alumina-silicate ceramic fibre as two class carcinogenic substance and limit production); The refractory fibre price is very high, particularly high temperature Al
2O
3Fibre product, the light high performance Al that produces as Britain MorganThermal Ceramics company and Japanese Aesop Lai Te company
2O
3Fiber composite is high temperature resistant insulating ceramic material, price at home is up to 550,000～600,000 yuans per ton.Therefore, for solving the problem that the traditional industry kiln exists with lightweight refractory, research and development novel light heat-insulating material is very necessary.
(its chemical formula is CaAl to calcium hexaluminate
12O
19Or CaO6Al
2O
3, be abbreviated as CA
6) be that the aluminium calcium with stronger anti-hydratability is high temperature resistant compound, fusing point is 1875 ℃, the coefficient of expansion is near Al
2O
3, be a kind of refractory materials that receives much attention at present.CA
6Belong to hexagonal system, perpendicular to the axial O of C
2-The velocity of diffusion ratio to be parallel to the axial velocity of diffusion of C fast, have the characteristic of preferential formation sheet or platelike crystal.At Al such as corundum-spinel, aluminous cement combined corundum, alumina-magnesia castables
2O
3In-MgO-CaO system the refractory materials, CA
6The reaction product under the hot conditions normally, its form of flake crystal be interspersed in corundum mutually or spinel mutually between, can improve the mechanical property of refractory materials, at high temperature can keep bigger specific surface area, good high temperature insulating effect can be arranged; Simultaneously good stability is arranged under high-temperature reductibility atmosphere, have alkali resistant erosional competency and slag corrosion resistance ability preferably.Existing at home and abroad at present much to CA
6The research of lagging material, and develop mature C A
6The porous material product, this material crystals similar has extremely low thermal conductivity in the fibrous texture of ceramic fiber.
Because CA
6Distinctive crystalline structure and character make it obtain paying attention to as the new type high temperature lagging material, lightweight calcium hexaluminate insulating refractory is a kind of novel light high-temperature heat insulation refractory materials, compare with traditional mullite lightweight refractory, has higher use temperature, the pore of micron order and submicron order, the microstructure of en plaque, lower thermal conductivity, low volume density, high chemical stability and good characteristics such as alkali resistant aggressiveness, can reduce accumulation of heat loss and heat lost by radiation as the high temperature modification ceramic kiln significantly with the lightweight insulating refractory, have a very important role for improving the net heat utilization ratio.Developed the calcium hexaluminate porous aggregate that can carry out industrial application at present both at home and abroad, domestic also the appearance is used for the report of aluminium refining with refractory materials with calcium hexaluminate, as Chinese invention patent " permeable fireproof materials for aluminium refining and preparation method thereof " (publication number: CN1884201A), but the light cinder brick that is used for high temperature kiln report not almost.Therefore the calcium hexaluminate lightweight brick of exploitation with independent intellectual property right energy-conservation significant to China's economic construction and high temperature industry.
Summary of the invention:
The present invention seeks at present kiln lining low with refractory fibre product intensity, the erosive wear performance of high temperature resistance Dual-Phrase Distribution of Gas olid (high-temperature flue gas and high-temperature flue gas/solid combustion particle) is relatively poor, there is carcinogenic risk in production and the use, the price height, common pure aluminium silicate light weight refractory brick, high alumina light weight refractory brick and alumina hollow ball refractory brick exist density higher, thermal conductivity is higher, heat storage capacity is bigger, the anti-thermal shock less stable, work-ing life is short, problem such as energy-saving effect difference in the use, utilize the low thermal conductivity of calcium hexaluminate, good stability under high-temperature reductibility atmosphere, alkali resistant erosional competency and slag corrosion resistance ability are better, feature of long life, a kind of calcium hexaluminate lightweight refractory brick and preparation method thereof is proposed, it is energy-efficient to reach preparation, the purpose of the light fire brick that long-life hot industry kiln lining is used, thus contribute for the energy-conservation of hot industry.
For achieving the above object, technical scheme of the present invention is as follows:
The present invention is a kind of calcium hexaluminate lightweight refractory brick and preparation method thereof, it is characterized in that: the main high temperature resistant thing of this refractory brick is the calcium hexaluminate phase mutually; The main chemical compositions of this refractory brick is: Al
2O
387.6%～91.6wt.%, CaO 8.3～10wt.%, other content of impurities is less than 5.0wt.%.
The used calcium source raw material of described preparation calcium hexaluminate can be industrial chemicals such as lime carbonate, calcium hydroxide or calcium oxide, also can be raw mineral materials (the Wingdale requirement CaCO that process high-temperature calcinations such as Wingdale or lime can generate calcium oxide
3〉=98.0%, lime (unslaked lime or white lime mainly contain calcium oxide or calcium hydroxide) requires calcium oxide or calcium hydroxide all 〉=98.0%) particle size of raw material is for less than 0.15mm.The used aluminium source raw material of described preparation calcium hexaluminate is aluminum oxide (α-Al
2O
3Or γ-Al
2O
3Can, require α-Al
2O
3〉=99.0%, γ-Al
2O
3〉=99.0%), aluminium hydroxide etc., the particle size of raw material is less than 0.15mm.
A kind of calcium hexaluminate lightweight refractory brick that the present invention proposes and preparation method thereof, it is characterized in that: described method at first is with after the stoichiometric batching of various raw materials according to calcium hexaluminate, mix earlier, be milled down to screen over-size less than the aperture sieve of 0.060mm then together less than 3.0wt.%; The powder that will take out from grinding machine adds and accounts for 0.1～18.0% of total batching and burn to lose pore-forming material and (burn and lose pore-forming material and can be chosen as wherein one or more of wood chip sawdust or other plant powder or polystyrene spheres or coke powder or coal powder or activated carbon etc. and can lose pore-forming material as burning burning the material that loses greater than 1000 ℃, its particle diameter≤3.0mm) mix together, add 6～30% drinkable water after mixing again and stir, the pug that obtains adopts vibrating casting manufacturing process be shaped (also available mud extruder extrusion molding or manual ramming or castable or machine moulding).Wet base after the shaping is seasoning 12～24h at room temperature, dries in 50～200 ℃ in dry kiln then.The adobe that drying is good is packed into and is burnt till in the kiln, 1450～1600 ℃ of final firing temperatures, to burn till the cooled adobe of kiln discharge on request size cut, promptly obtain low thermal conductivity of the present invention, better, the long-life calcium hexaluminate lightweight refractory brick of good stability, alkali resistant erosional competency and slag corrosion resistance ability under high-temperature reductibility atmosphere.The correlated performance of this calcium hexaluminate lightweight refractory brick reaches: volume density≤0.48g/cm
3, 400 ℃ of thermal conductivity≤0.10w/mk, 800 ℃ of thermal conductivity≤0.15w/mk, folding strength 〉=1.0MPa, compressive strength 〉=1.2MPa.
Embodiment:
Below in conjunction with embodiment technical scheme of the present invention is described further:
Raw material of the present invention is: the used calcium source raw material of described preparation calcium hexaluminate can be industrial chemicals such as lime carbonate, calcium hydroxide or calcium oxide, also can be raw mineral materials (the Wingdale requirement CaCO that process high-temperature calcinations such as Wingdale or lime can generate calcium oxide
3〉=98.0%, lime (unslaked lime or white lime mainly contain calcium oxide or calcium hydroxide) requires calcium oxide or calcium hydroxide all 〉=98.0%) particle size of raw material is less than 0.15mm.The used aluminium source raw material of described preparation calcium hexaluminate is aluminum oxide (α-Al
2O
3Or γ-Al
2O
3Can, require α-Al
2O
3〉=99.0%, γ-Al
2O
3〉=99.0%), aluminium hydroxide etc., the particle size of raw material is less than 0.15mm.
A kind of calcium hexaluminate lightweight refractory brick that the present invention proposes and preparation method thereof, it is characterized in that: described method at first is with after the stoichiometric batching of various raw materials according to calcium hexaluminate, mix earlier, be milled down to screen over-size less than the aperture sieve of 0.060mm then together less than 3.0wt.%; The powder that will take out from grinding machine adds and accounts for 0.1～18.0% of total batching and burn to lose pore-forming material and (burn and lose pore-forming material and can be chosen as wherein one or more of wood chip sawdust or other plant powder or polystyrene spheres or coke powder or coal powder or activated carbon etc. and can lose pore-forming material as burning burning the material that loses greater than 1000 ℃, its particle diameter≤3.0mm) mix together, add 6～30% drinkable water after mixing again and stir, the pug that obtains adopts vibrating casting manufacturing process be shaped (also available mud extruder extrusion molding or manual ramming or castable or machine moulding).Wet base after the shaping is seasoning 12～24h at room temperature, dries in 50～200 ℃ in dry kiln then.The adobe that drying is good is packed into and is burnt till in the kiln, 1450～1600 ℃ of final firing temperatures, to burn till the cooled adobe of kiln discharge on request size cut, promptly obtain low thermal conductivity of the present invention, better, the long-life calcium hexaluminate lightweight refractory brick of good stability, alkali resistant erosional competency and slag corrosion resistance ability under high-temperature reductibility atmosphere.
A kind of preparation technology's flow process of calcium hexaluminate lightweight refractory brick is:
Raw material → batching → dry ball milling → add pore-forming material → stirring → shaping → drying → burn till → process → check
Embodiment 1
Raw material and proportioning:
(require CaCO with lime carbonate
3〉=98.0%) be the calcium source, aluminium hydroxide (requires Al (OH)
3〉=99.0%) be the aluminium source, the particle size of raw material is less than 0.15mm.
Batching, levigate:
At first various raw materials are packed into according to the stoichiometric of calcium hexaluminate and be milled down to screen over-size less than the aperture sieve of 0.060mm in the grinding machine less than 3.0wt.%.
Add pore-forming material and stir shaping:
Add the polystyrene spheres that accounts for total batching 8.0%, the wood chip sawdust of total batching 4.0% (requires its particle diameter≤3.0mm), the compound that ball milling is good mixed 10 minutes with polystyrene spheres, wood chip sawdust, add 6% drinkable water again and stirred the pug that obtains pressurization and vibration castable 5 minutes.
Dry:
Wet base after the shaping is seasoning 12h at room temperature, then in dry kiln prior to 100 ℃ of dry 4h, in 200 ℃ of oven dry 8h, make water ratio≤3.0% of green compact again.
Burn till:
The adobe that drying is good is packed into and is burnt till in the kiln, 1500 ℃ of final firing temperatures.Calcining system is: 900 ℃ of insulation 4h, 1100 ℃ of insulation 4h, 1500 ℃ of insulation 3h.
Processing, check:
With the adobe after burning till on request size cut and promptly obtain corresponding calcium hexaluminate lightweight refractory brick.
The main performance index of resulting product is as follows:
Suitable use temperature: 1600 ℃; Volume density: 0.47g/cm
3Strength at normal temperature 1.6MPa; Cold crushing strength: 2.0MPa; 400 ℃ of thermal conductivitys are 0.08w/mk, and 800 ℃ of thermal conductivitys are 0.15w/mk.
Embodiment 2
Raw material and proportioning:
With calcium oxide (requiring CaO 〉=98.0%) is the calcium source, γ-Al
2O
3(require Al
2O
3〉=99.0%) be the aluminium source, the particle size of raw material is less than 0.15mm.
Batching, levigate:
At first with various raw materials according to the stoichiometric of the calcium hexaluminate ball mill ball milling 12h that packs into, raw material is milled down to screen over-size less than the aperture sieve of 0.060mm less than 3.0wt.%.
Add pore-forming material and stir shaping:
Add and to account for the coke powder of total batching 6% and 8% polystyrene spheres and (require its particle diameter≤3.0mm), the compound that ball milling is good mixed 10 minutes with polystyrene spheres, add 6% drinkable water again and stirred the pug that obtains pressurization and vibration castable 5 minutes.
Dry:
Wet base after the shaping is seasoning 12h at room temperature, then in dry kiln prior to 100 ℃ of dry 4h, in 200 ℃ of oven dry 8h, make water ratio≤3.0% of green compact again.
Burn till:
The adobe that drying is good is packed into and is burnt till in the kiln, 1550 ℃ of final firing temperatures.Calcining system is: 900 ℃ of insulation 4h, 1100 ℃ of insulation 4h, 1550 ℃ of insulation 3h.
Processing, check:
With the adobe after burning till on request size cut and promptly obtain corresponding calcium hexaluminate lightweight refractory brick.
The main performance index of resulting product is as follows:
Suitable use temperature: 1650 ℃; Volume density: 0.46g/cm
3Strength at normal temperature 1.4MPa; Cold crushing strength: 2.0MPa; 400 ℃ of thermal conductivitys are 0.09w/mk, and 800 ℃ of thermal conductivitys are 0.14w/mk.
Embodiment 3
Raw material and proportioning:
(require CaCO with lime carbonate
3〉=98.0%) is the calcium source, γ-Al
2O
3(require Al
2O
3〉=99.0%) be the aluminium source, the particle size of raw material is less than 0.15mm.
Batching, levigate:
At first with various raw materials according to the stoichiometric of the calcium hexaluminate ball mill ball milling 12h that packs into, raw material is milled down to screen over-size less than the aperture sieve of 0.060mm less than 3.0wt.%.
Add pore-forming material and stir shaping:
Add and to account for 10.0% coke powder of total batching and 4.0% wood chip sawdust and (require its particle diameter≤3.0mm), compound was mixed 30 minutes with coke powder, add 13% drinkable water again and stirred 5 minutes, the pug that obtains is shaped with vibrating casting and obtains base substrate.
Dry:
Wet base after the shaping is seasoning 12h at room temperature, then in dry kiln prior to 100 ℃ of dry 4h, in 200 ℃ of oven dry 8h, make water ratio≤3.0% of green compact again.
Burn till:
The adobe that drying is good is packed into and is burnt till in the kiln, 1580 ℃ of final firing temperatures.Calcining system is: 900 ℃ of insulation 4h, 1100 ℃ of insulation 4h, 1580 ℃ of insulation 3h.
Processing, check:
With the adobe after burning till on request size cut and promptly obtain corresponding calcium hexaluminate lightweight refractory brick.
The main performance index of resulting product is as follows:
Suitable use temperature: 1700 ℃; Volume density: 0.45g/cm
3Strength at normal temperature 1.2MPa; Cold crushing strength: 1.8MPa; 400 ℃ of thermal conductivitys are 0.07w/mk, and 800 ℃ of thermal conductivitys are 0.12w/mk.
Claims (3)
1. the present invention is a kind of calcium hexaluminate lightweight refractory brick and preparation method thereof, it is characterized in that: the main high temperature resistant thing of this refractory brick is the calcium hexaluminate phase mutually; The main chemical compositions of this refractory brick is: Al
2O
387.6%～91.6wt.%, CaO 8.3～10wt.%, other content of impurities is less than 5.0wt.%.
2. calcium hexaluminate lightweight refractory brick as claimed in claim 1, it is characterized in that: the used calcium source raw material of described preparation calcium hexaluminate can be industrial chemicals such as lime carbonate, calcium hydroxide or calcium oxide, also can be raw mineral materials (the Wingdale requirement CaCO that process high-temperature calcinations such as Wingdale or lime can generate calcium oxide
3〉=98.0%, lime (unslaked lime or white lime mainly contain calcium oxide or calcium hydroxide) requires calcium oxide or calcium hydroxide all 〉=98.0%) particle size of raw material is for less than 0.15mm.The used aluminium source raw material of described preparation calcium hexaluminate is aluminum oxide (α-Al
2O
3Or γ-Al
2O
3Can, require α-Al
2O
3〉=99.0%, γ-Al
2O
3〉=99.0%), aluminium hydroxide etc., the particle size of raw material is less than 0.15mm.
3. method for preparing as claim 1 and 2 described calcium hexaluminate lightweight refractory bricks, it is characterized in that: described method at first is with after the stoichiometric batching of various raw materials according to calcium hexaluminate, mix earlier, be milled down to screen over-size less than the aperture sieve of 0.060mm then together less than 3.0wt.%; The powder that will take out from grinding machine adds and accounts for 0.1～18.0% of total batching and burn to lose pore-forming material and (burn and lose pore-forming material and can be chosen as wherein one or more of wood chip sawdust or other plant powder or polystyrene spheres or coke powder or coal powder or activated carbon etc. and can lose pore-forming material as burning burning the material that loses greater than 1000 ℃, its particle diameter≤3.0mm) mix together, add 6～30% drinkable water after mixing again and stir, the pug that obtains adopts vibrating casting manufacturing process be shaped (also available mud extruder extrusion molding or manual ramming or castable or machine moulding).Wet base after the shaping is seasoning 12～24h at room temperature, dries in 50～200 ℃ in dry kiln then.The adobe that drying is good is packed into and is burnt till in the kiln, 1450～1600 ℃ of final firing temperatures, to burn till the cooled adobe of kiln discharge on request size cut, promptly obtain low thermal conductivity of the present invention, better, the long-life calcium hexaluminate lightweight refractory brick of good stability, alkali resistant erosional competency and slag corrosion resistance ability under high-temperature reductibility atmosphere.
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| CN103553101A (en) * | 2013-08-26 | 2014-02-05 | 西南科技大学 | Method for preparing lightweight calcium hexaaluminate at low temperature |
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| CN104650821A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Solid particle blocks for chemical heat storage |
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Application publication date: 20101229 |