CN101367663B - Melt-out recombined composite aluminum oxide refractory materials - Google Patents
Melt-out recombined composite aluminum oxide refractory materials Download PDFInfo
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- CN101367663B CN101367663B CN2008101688193A CN200810168819A CN101367663B CN 101367663 B CN101367663 B CN 101367663B CN 2008101688193 A CN2008101688193 A CN 2008101688193A CN 200810168819 A CN200810168819 A CN 200810168819A CN 101367663 B CN101367663 B CN 101367663B
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Abstract
The invention relates to a melting recombined composite alumina fire proof material, which is characterized in that the formula of the fire proof material comprises: 48 to 56 percent of 5-1mm alpha beta alumina or beta alumina, 12 to 22 percent of 1-0.088mm alpha beta alumina or beta alumina, 16 to 25 percent of d90<0.088mm alpha beta alumina or beta alumina, 0 to 12 percent of d95<0.020mm beta alumina micro powder, 0 to 5 percent of alpha alumina micro powder, 2 to 7 percent of alumina hydrate, 0.5 to 5 percent of magnesium additive, 0.05 to 0.4 percent of plus super-plasticizer, 1 to 6 percent of plus polypropylene acid series latex and 1 to 6 percent of plus water. Goods made by the invention have good manufacturing performance and good high temperature proof performance, and are suitable to be used as fire proof materials of large-sized and special-shaped fire proof products, a regenerator lattice body, and the like of the upper structure of a glass kiln.
Description
Technical field
The present invention is that a kind of fusion is again in conjunction with compound α β or βYang Hualv refractory materials, its manufacturing processed is: electric smelting α βYang Hualv or electric smelting βYang Hualv raw material pulverizing, screening, levigate after, but with αYang Hualv micro mist ALUMINA HYDRATE, magnesia auxiliary agent, polyacrylic acid emulsion, chemical admixture and water cooperates, prefabricated component is made in stirring, shaping, the demoulding, maintenance, drying process, burn till through high temperature again and make with Na Mg-β "
Ss(Na
1.51Mg
0.69Al
10.370
17) be in conjunction with phase, with alpha-beta alumina or βYang Hualv (Na
2O11Al
2O
3Or NaAl
11O
17) be the refractory materials of principal crystalline phase.This material has good shaping, the demoulding, sintering character, and has special outstanding high temperature resistance, is suitable as refractory materialss such as large-scale, the special shape refractory product of glass kiln superstructure and regenerator lattice and uses.
Background technology
Modern glass kiln need use a large amount of founding aluminium oxide refractory materials.Wherein, founding α-βYang Hualv refractory materials contains 45% Alpha-alumina and 55% beta-alumina approximately, and about 1% impurity mutually and 2% pore.Founding beta-alumina refractory materials mainly is made up of big crystal grain beta-alumina, and impurity can be ignored void content about 4% mutually.Founding α, beta-alumina or beta-alumina material do not contain glassy phase, do not have the infusibility crystalline phase again, can not produce detrimentally affect to glass quality, also have good resistibility in the erosion to soda-lime glass or alkali steam below 1350 ℃.Therefore, α, β-alumina material are widely used in the part of glass kiln cooling end contact glass metal.β-alumina material then is widely used in the superstructure that cooling end does not have the dust position.
At present, full-oxygen combustion is the developing direction of glass kiln.After adopting pure oxygen combustion technology, can improve quality, the minimizing fuel consumption of glass, avoid getting rid of obnoxious flavour NOx, save the spending of building regenerator and handling objectionable constituent in the gas.But during comburant oxygen, the concentration of NaOH greatly increases in the products of combustion, causes Na
2O is to containing SiO
2The strong corrosion of refractory materials.Therefore, oxy-fuel glass furnace needs to use α-βYang Hualv and βYang Hualv refractory materials more.
Now, make founding α-βYang Hualv or founding βYang Hualv syphon by casting method usually, its temperature of fusion height, the production qualification rate is low and be difficult to processed shaping.Especially, the production efficiency of oversize or special shape casting product is very low.Because heat radiation is irregular, can produce very big thermal stresses in the cooling, very easily make these material damage, thereby cause very expensive production cost.
Generally, be difficult to ordinary method and make sintering α-βYang Hualv or βYang Hualv material, particularly make large size or special odd-shaped goods.On the one hand, the difficult shaping of this class refractory materials, hard-to-sinter.On the other hand, though can utilize pure calcium aluminate cement, water glass, clay to make large size or special shape βYang Hualv goods for wedding agent.But the impurity that these materials are brought into meeting and βYang Hualv reaction generate eutectic, and this will make the high thermal resistance of goods and erosion-resisting characteristics all be subjected to grievous injury.
At present, vast glassworks man presses for the technology that refractory materials scientific and technical personnel development makes new advances, and produces founding aluminium oxide refractory material more, particularly is difficult to large-scale, the special shape fire resistive material product of making.
Summary of the invention
The objective of the invention is to invent a kind of melt-out recombined composite aluminum oxide refractory materials.The contriver has proposed a new technology: but normal temperature by polyacrylic acid and ALUMINA HYDRATE, contain the reaction of magnesium oxide material, generate polyacrylic acid aluminium (magnesium) polymer and produce combination.After the thermal treatment, above-mentioned polymer decomposes, and organic constituent burns and loses, and inorganic component becomes activated alumina, activated magnesia, again sintering in addition.Like this, just greatly reduce the difficulty of making large-scale, special shape fire resistive material product.Products made thereby of the present invention has good manufacturing property and outstanding high temperature resistance very.
Relevant chemical reaction is as follows:
At first, room temperature is carried out ρ Al
2O
3With the aquation of MgO, and Al (OH)
3, Mg (OH)
2With polyacrylic chemical reaction.By reaction, 1)-4) high volence metal ion Al, Mg replace the H on the emulsion carboxyl, and glue connects a plurality of polyacrylic acid molecules and forms the bigger polyacrylic acid aluminium (magnesium) of molecular weight.ρ aluminum oxide or magnesium oxide also may direct and polyacrylic acid reactions.This is the principle that produces physical strength after condensation of materials, sclerosis and the oven dry, sees following various:
ρAl
2O
3+3H
2O＝2Al(OH)
3 1)
MgO+H
2O＝Mg(OH)
2 2)
Al(OH)
3+3R-COOH＝(R-COO)
3Al+1.5H
2O 3)
Mg(OH)
2+2R-COOH＝(R-COO)
2Mg+H
2O 4)
Hot, the decomposition of polyacrylic acid aluminium (magnesium) before this, organic burning is lost, and is MgO and Al then
2O
3Reaction forms magnesium-aluminium spinel, and forms Na, Mg-β " ss (Na
1.51Mg
0.69Al
10.370
17).Na, Mg-β " ss can be by Na-β " (NaAl
6O
10) molten admittedly MA and Na
2O forms; Na, Mg-β " ss also can be by βYang Hualv (NaAl
11O
17) form with MgO or MA reaction.The relevant formula as follows of reacting:
0.69MgO+0.755Na
2O11Al
2O
3＝Na
1.51Mg
0.69Al
10.37O
17+3.12Al
2O
3 5.1)
MgO+AL
2O
3＝MgOAL
2O
3 5.2.1)
0.69MgOAL
2O
3+0.755Na
2O11Al
2O
3＝Na
1.51Mg
0.69Al
10.37O
17+3.81Al
2O
3 5.2.2)
β-Al
2O
3-α-Al
2O
3-Na, Mg-β " ss (Na
1.51Mg
0.69Al
10.370
17) initial melting temperature of phase region is greater than 1680 ℃, belongs to the extremely fireproof system.So, material of the present invention through batching, companion and, shaping, maintenance, the demoulding, drying and burn till after can obtain the high thermal resistance of excellence.
Because of the purity extra-high-speed, the α βYang Hualv is corresponding with the βYang Hualv material to have very high sintering temperature.If temperature is low, material can not sintering.If the temperature height, Na
2The O volatile material can not sintering.Help burning if mix the silicon ash, the silicon ash will form eutectic material-nepheline with the βYang Hualv reaction.Help burning if admixture contains the material of CaO, these materials also will form eutectic material-C
3N
2A
5If admixture MgO does not form eutectic, but middle temperature burning back intensity is extremely low.When being heat-treated to 1000 ℃ of left and right sides, low temperature bond is decomposed mutually already, and pottery is not in conjunction with producing as yet, and the bonding force in the matrix is very weak.At this moment, MgO and Al
2O
3Solid state reaction takes place, form magnesium-aluminium spinel, producing expands will influence the medium temperature intensity of sample, even the qualification rate of product.
So the present invention creatively proposes and replace magnesia as being shaped and sintering aid with the activated carbon aluminate.On the one hand, the activated carbon aluminate can part aquation, form polyacrylic acid aluminium (magnesium) polymer of some amount, guarantee to condense, sclerosis and demolding performace.On the other hand, add pre-synthetic MgAl spinal and just can avoid forming the volumetric expansion that magnesium-aluminium spinel is followed, thereby temperature is burnt back intensity in significantly improving, and significantly reduce sintering temperature.Like this, with regard to the ingenious problem that has solved α βYang Hualv or βYang Hualv material hard-to-sinter.
In view of the above, prescription of the present invention is:
5-1mm α βYang Hualv or βYang Hualv 48-56%
1-0.088mm α βYang Hualv or βYang Hualv 12-22%
d
90＜0.088mm α βYang Hualv or βYang Hualv 16-25%
d
95＜0.020mm βYang Hualv micro mist 0-12%
αYang Hualv micro mist 0-5%
But ALUMINA HYDRATE 2-7%
Magnesia auxiliary agent 0.5-5%
Add high efficiency water reducing agent (poly carboxylic acid+sulfonated naphthalene yuban+sulfonated melamine polymkeric substance) 0.05-0.4%
Add polyacrylic emulsion 1-6%
Add water 1-6%
The feature of above-mentioned raw materials:
Described α βYang Hualv is that electric smelting α βYang Hualv material (as the waste product of founding α βYang Hualv) makes.
Described βYang Hualv is that electric smelting βYang Hualv material (as the waste product of founding βYang Hualv) makes.
Described particle diameter d
90Or d
95Be respectively and account for total amount 90% small-particle and account for total amount 10% oarse-grained boundary size in the powder, or account for total amount 95% small-particle and account for total amount 5% oarse-grained boundary size.
Described αYang Hualv micro mist is commercially available prod d
50=8-2 μ m.
But described ALUMINA HYDRATE is the commercially available prod, and its principal constituent is ρ-Al
2O
3The mixture of the steady alpha-alumina crystals of Jie.
Described magnesia auxiliary agent can be magnesia powder (＜0.088mm content〉90% or magnesia micro mist (＜0.020mm content〉95%), any mixture of activated carbon aluminate (＜0.020mm content〉95%).Preferably main component is the activated carbon aluminate.This auxiliary agent plays and improves curing speed and improve the agglomerating effect." very low temperature prepares the technology of active synthetic refractory raw material " (Chinese invention patent CN 01118014.5) that this spinel can adopt the author to propose makes.
Described high efficiency water reducing agent is commercially available cement water reducing agent, comprises sulfonated naphthalene yuban high efficiency water reducing agent and sulfonated melamine polymer high efficiency water reducer, and any cooperation of polycarboxylic acid series high efficiency water reducing agent.
Described polyacrylic emulsion is commercially available building polyacrylic acid emulsion, comprises building polyacrylic acid emulsion, building vinylformic acid and acrylate copolymer emulsion and vinylformic acid-acrylate-styrene terpolymer non-ionic water-soluble emulsion.The solids content 40-60% of emulsion, typical particle diameter 0.1-0.3 μ m, pH value 6-9.
Melt-out recombined composite aluminum oxide brick main component: Al
2O
391-96%, Na
2O3-7%, MgO0.2-3.5%, SiO
20.1-0.5%.
Each raw material makes base substrate through mixing, shaping, maintenance by above proportioning weighing, drying again through 1430-1650 ℃ burn till, operation such as check makes large-scale or special odd-shaped fire resistive material product.
Embodiment
Embodiment 1
Adopt 5-1mm electric smelting α βYang Hualv 53%, 1-0.088mm electric smelting α βYang Hualv 17%, d
90＜0.088mm electric smelting α βYang Hualv 17%, d
95＜0.020mm electric smelting βYang Hualv micro mist 4%, d
95＜0.020mm alumina powder 2%, activated carbon aluminate micro mist 3%, but ALUMINA HYDRATE 4%,, add polycarboxylate water-reducer 0.1%, polyacrylic acid emulsion 3%, water 3% back companion and, obtain the slurry of good fluidity.After the shaping, slurry condensed in 0.5 hour, solidified in 2 hours, can the demoulding after 12-16 hours.Through 110 ℃ * 24H drying, sample obtains the folding strength of 8MPa, the compressive strength of 35MPa; Obtain the folding strength of 12MPa again through thermal treatment in 1500 ℃ * 3 hours, the compressive strength of 71MPa is burnt till line and is changed to 0.6%, refractoriness under load T
0.61700 ℃.
Products made thereby has good manufacturing property and outstanding high temperature resistance very, and experiment has obtained success.
Embodiment 2
Adopt 5-1mm electric smelting βYang Hualv 50%, 1-0.088mm electric smelting βYang Hualv 20%, d
90＜0.088mm electric smelting βYang Hualv 17%, d
95＜0.020mm electric smelting βYang Hualv micro mist 4%, activated carbon aluminate micro mist 4%, but ALUMINA HYDRATE 5%,, add polycarboxylate water-reducer 0.1%, polyacrylic acid emulsion 3%, water 3% back companion and, obtain the slurry of good fluidity.After the shaping, slurry condensed in 2 hours, solidified in 8 hours, can the demoulding after 24 hours.Through 110 ℃ * 24H drying, sample obtains the folding strength of 10MPa, the compressive strength of 45MPa; Can obtain through thermal treatment in 1100 ℃ * 3 hours the compressive strength of 12MPa, the light sample of mixing magnesia improves nearly 200%; Obtain the folding strength of 16MPa again through thermal treatment in 1500 ℃ * 3 hours, the compressive strength of 80MPa is burnt till line and is changed to 0.5%, refractoriness under load T
0.61700 ℃.
Products made thereby of the present invention has good manufacturing property and outstanding high temperature resistance very, is suitable as refractory materialss such as large-scale, the special shape refractory product of glass kiln superstructure and regenerator lattice and uses.
Claims (2)
1. melt-out recombined composite aluminum oxide refractory materials, it is characterized in that: described refractory materials prescription is:
Described α βYang Hualv is that electric smelting α βYang Hualv material makes;
Described βYang Hualv is that electric smelting βYang Hualv material makes;
Described particle diameter d
90Or d
95Be respectively and account for total amount 90% small-particle and account for total amount 10% oarse-grained boundary size in the powder, or account for total amount 95% small-particle and account for total amount 5% oarse-grained boundary size;
Described αYang Hualv micro mist is commercially available prod d
50=8-2 μ m;
But described ALUMINA HYDRATE is the commercially available prod, and its principal constituent is ρ-Al
2O
3The mixture of the steady alpha-alumina crystals of Jie;
Described magnesia auxiliary agent is＜magnesia powder of 0.088mm content＞90% or＜the magnesia micro mist of 0.020mm content＞95%,＜any mixture of the activated carbon aluminate of 0.020mm content＞95%;
Described high efficiency water reducing agent is commercially available cement water reducing agent, comprises sulfonated naphthalene yuban high efficiency water reducing agent and sulfonated melamine polymer high efficiency water reducer, and any cooperation of polycarboxylic acid series high efficiency water reducing agent;
Described polyacrylic emulsion is commercially available building polyacrylic acid emulsion, comprise building polyacrylic acid emulsion, building vinylformic acid and acrylate copolymer emulsion and vinylformic acid-acrylate-styrene terpolymer non-ionic water-soluble emulsion, the solids content 40-60% of emulsion, typical particle diameter 0.1-0.3 μ m, pH value 6-9;
Described melt-out recombined composite aluminum oxide brick main component: Al
2O
391-96%, Na
2O 3-7%, MgO 0.2-3.5%, SiO
20.1-0.5%.
2. make the described refractory materials production technique of claim 1 for one kind, above-mentioned each raw material makes base substrate by above proportioning weighing through mixing, shaping, maintenance, drying, burns till, checks and make, and it is characterized in that: firing temperature 1430-1650 ℃.
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|---|---|---|---|
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| CN101367663B true CN101367663B (en) | 2011-08-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708997B (en) * | 2009-11-10 | 2012-05-23 | 武汉科技大学 | Alumina light-weight brick and preparation method thereof |
| CN101948300B (en) * | 2010-08-26 | 2013-01-16 | 武汉科技大学 | Corundum-spinel lightweight heat-insulating material and preparation method thereof |
| DE102016224443A1 (en) | 2016-12-08 | 2018-06-14 | Siemens Aktiengesellschaft | Erosion-resistant ceramic material, powder, slurry and component |
| CN107162611A (en) * | 2017-05-26 | 2017-09-15 | 长兴华悦耐火材料厂 | The resource recycle method of carbon containing waste and old refractory brick |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109035A (en) * | 1994-12-22 | 1995-09-27 | 沈阳耐火材料厂 | Method for increasing finished product rate of fusion-cast alpha-beta aluminum oxide bricks |
| EP0895973B1 (en) * | 1997-08-08 | 2001-11-21 | Societe Europeenne Des Produits Refractaires | Refractory material of beta-alumina |
| CN1939875A (en) * | 2006-09-07 | 2007-04-04 | 浙江大学 | Thermal-knock resisting diamond spar-spinele refractory materials and its production |
-
2008
- 2008-09-28 CN CN2008101688193A patent/CN101367663B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109035A (en) * | 1994-12-22 | 1995-09-27 | 沈阳耐火材料厂 | Method for increasing finished product rate of fusion-cast alpha-beta aluminum oxide bricks |
| EP0895973B1 (en) * | 1997-08-08 | 2001-11-21 | Societe Europeenne Des Produits Refractaires | Refractory material of beta-alumina |
| CN1939875A (en) * | 2006-09-07 | 2007-04-04 | 浙江大学 | Thermal-knock resisting diamond spar-spinele refractory materials and its production |
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