CN102584269A - Refractory material granules with aluminum titanate coatings and preparation method thereof - Google Patents
Refractory material granules with aluminum titanate coatings and preparation method thereof Download PDFInfo
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- CN102584269A CN102584269A CN2012100071328A CN201210007132A CN102584269A CN 102584269 A CN102584269 A CN 102584269A CN 2012100071328 A CN2012100071328 A CN 2012100071328A CN 201210007132 A CN201210007132 A CN 201210007132A CN 102584269 A CN102584269 A CN 102584269A
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Abstract
The invention discloses refractory material granules and a preparation method thereof. The preparation method comprises the following steps of: preparing titanium sol, titanium-aluminum composite sol, aluminum titanate powder slurry, and performing surface coating and heat treatment on the refractory material granules, so that a layer of aluminum titanate covers the surfaces of the refractory material granules. The aluminum titanate has the characteristic of not infiltrating aluminum, so the treated refractory material granules do not infiltrate the aluminum. The titanium sol, the titanium-aluminum composite sol and the aluminum titanate powder slurry enter cracks and holes of the refractory material granules to repair the cracks and the holes after high-temperature sintering, so that the compression strength of the refractory material granules is improved.
Description
Technical field
The present invention relates to a kind of fire resisting material particle and preparation method thereof, especially relate to a kind of fire resisting material particle and preparation method that the aluminium titanates coating is arranged.
Background technology
Along with the rapid growth of China to the non-ferrous metal demand; Coloured smelting factory is constantly adopted new technology and new technology; The maximization and the high efficiency that make non-ferrous metallurgical furnace are to adapt to requirements of the times, and this just makes that the working conditions of refractory materials is more and more harsh, and refractory materials has been proposed many new requirements; Selecting for use of refractory materials becomes one of key link in the production, and the molten metal contact site all adopts fine and close high quality refractory materials in the Non Ferrous Melting Furnace.
With the metallurgy of aluminium is example, and molten aluminium stove adopts starting material such as compact high-alumina alumina commonly used, fused alumina, sintered alumina, adds permeability-reducing admixtures such as silit, aluminium titanates, Calcium Fluoride (Fluorspan), permanent white, and is not only with high costs, and thermal conductivity is high, serious heat loss; If employing lightweight material and low-cost high silicon raw material then are prone to aluminising or react with aluminum melt, it is required that performance is difficult to satisfy production.If the aluminium titanates of anti-aluminum solutions infiltration of these raw material surface applied one decks or reaction just can address these problems well.The light matter aggregate of introducing can reduce the goods thermal conductivity significantly as furnace charge in this external nonferrous metallurgy, reduces energy consumption; Help carrying out the great strategy of national energy-saving and emission-reduction; And can increase substantially the goods thermal shock performance, and increase the service life, reduce use cost.Aglite surface forms one deck aluminium titanates also can increase substantially its compressive strength, is example with the alumina hollow ball, and through behind surface formation aluminium titanates, its intensity is original more than three times.
Summary of the invention
The object of the present invention is to provide a kind of fire resisting material particle and preparation method that the aluminium titanates coating is arranged, utilize existing fire resisting material particle, make the fire resisting material particle surface have one deck cannot not possess stickingly the method for the aluminium titanates of aluminium characteristic as starting material.
For achieving the above object, the step of the technical scheme that the present invention adopts is following:
One, a kind of fire resisting material particle: one deck aluminium titanates is arranged in the fire resisting material particle surface coverage; Massfraction is 0.05～50% aluminium titanates.
Described fire resisting material particle is compact refractory material particle or lightweight refractory particle, and fire resisting material particle is of a size of 1 micron～15 centimetres.
Described compact refractory material particle is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel; Magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, ferrochrome slag or slag.
Described lightweight refractory particle is alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball, floats pearl or expanded vermiculite.
Two: a kind of preparation method of fire resisting material particle, the step of this method is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 fire resisting material particle is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the fire resisting material particle surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the fire resisting material particle of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
Described fire resisting material particle is compact refractory material particle or lightweight refractory particle, and fire resisting material particle is of a size of 1 micron～15 centimetres.
Described compact refractory material particle is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, magnesite clinker, electrosmelted magnesite clinker, forsterite, serpentine, scum or slag.
Described lightweight refractory particle is alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball, floats pearl, haydite, perlite or expanded vermiculite.
The beneficial effect that the present invention has is:
Adopt and soak or spraying titanium colloidal sol, titanium aluminium complex sol is after the method for aluminium titanates powdery pulp is carried out surface-treated to fire resisting material particle; Titanium colloidal sol, titanium aluminium complex sol and aluminium titanates powdery pulp can be attached to the surfaces of fire resisting material particle, and get into the slit; In crackle and the hole, dry back titanium colloidal sol, titanium aluminium complex sol; The aluminium titanates powdery pulp is distributed in the fire resisting material particle surface, slit and intergranule.Under the condition of being heated, titanium glue and aluminum oxide fire resisting material particle matrix generate aluminium titanates; Titanium aluminium complex sol directly generates aluminium titanates at fire resisting material particle; Aluminum titanate body slurry then direct sintering is surperficial at fire resisting material particle.Because aluminium titanates has not imbibition characteristic of pair aluminium liquid, thereby treated fire resisting material particle does not soak into aluminium liquid.And titanium colloidal sol, titanium aluminium complex sol, aluminium titanates powdery pulp get among table fire resisting material particle crackle and the hole, generate aluminium titanates ability mended crack and hole behind the high temperature sintering, thereby improve the compressive strength of fire resisting material particle.Figure of description
Fig. 1 is an amorphous refractory uniform particles distribution plan.
Fig. 2 is an amorphous refractory granule partial sectional view.
Fig. 3 is spherical fire resisting material particle sectional view.
Among the figure: 1, amorphous refractory particle, 2, refractory material matrix, 3, amorphous refractory aluminium titanates coating, 4, spherical refractory material matrix, 5, spherical refractory materials aluminium titanates coating
Embodiment
Embodiment 1 (titanium colloidal sol)
Prepare titanium colloidal sol: Ti earlier
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer.The fire resisting material particle that forms the aluminium titanates coating to need on the surface then put into colloidal sol soak 0.5～60 minute after oven dry or colloidal sol is sprayed on fire resisting material particle surface to the moistening back that needs to form the aluminium titanates coating on the surface dries; Fire resisting material particle after will handling is then put into High Temperature Furnaces Heating Apparatus thermal treatment; Thermal treatment temp is 1250～1450 ℃; Soaking time 1～4 hour; Obtaining the surface has the fire resisting material particle of aluminium titanates coating, because aluminium titanates possesses and is not stained with the aluminium characteristic, is not stained with the aluminium characteristic so the refractory materials after handling possesses.Specific embodiments is seen table 1.Amorphous refractory size distribution such as Fig. 1 before being untreated, wherein 1 is alumine, alundum, fused corundom.Use this method gained surface that its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 of one deck Calcium Fluoride (Fluorspan) are arranged, wherein 2 is alumine, alundum, fused corundom, the 3rd, and the metatitanic acid aluminium lamination; With this method gained surface its part sectioned view of spherical fire resisting material particle such as Fig. 3 of one deck aluminium titanates are arranged, wherein 3 is metatitanic acid aluminium laminations, the 4th, and alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball or float the pearl matrix.
The sol-gel modified fire resisting material particle of table 1 titanium is handled under differing temps
Embodiment 2 (titanium aluminium complex sol)
Prepare titanium aluminium complex sol: Ti earlier
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer.Need are formed the aluminium titanates coating on the surface fire resisting material particle material is put into that colloidal sol soaks 0.5～60min or colloidal sol is sprayed on and needs to form aluminium titanates coating refractory particle surface on the surface and to surface wettability, dry; Put into High Temperature Furnaces Heating Apparatus thermal treatment then; Thermal treatment temp is 1250～1450 ℃; Soaking time 1～4 hour obtains the fire resisting material particle that there is the aluminium titanates coating on the surface, and specific embodiments and effect are seen table 2.Amorphous refractory size distribution such as Fig. 1 before being untreated, wherein 1 silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel, magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, slag, ferrochrome slag or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck aluminium titanates is arranged with this method gained surface; Wherein 2 is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel, magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, slag, ferrochrome slag or expanded vermiculite matrix, the 3rd, and the metatitanic acid aluminium lamination; With this method gained surface its part sectioned view of spherical fire resisting material particle such as Fig. 3 of one deck Calcium Fluoride (Fluorspan) are arranged, wherein 3 is metatitanic acid aluminium laminations, the 4th, and alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball or float the pearl matrix.
Table 2 titanium aluminium complex sol modification fire resisting material particle is handled under differing temps
Embodiment 3 (aluminium titanates powder)
Prepare the aluminium titanates powdery pulp: get the raw materials ready by the requirement of aluminium titanates quality mark, consist of massfraction and be 40～50% Al at present
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer.The fire resisting material particle that need is formed the aluminium titanates coating on the surface soaks 0.5～60min after drying in aluminium titanates powder slurry; Or the aluminium titanates powdery pulp is sprayed on needs to form on the refractory materials of aluminium titanates coating to the surface wettability after drying on the surface; Put into High Temperature Furnaces Heating Apparatus thermal treatment, thermal treatment temp is 1250～1450 ℃, soaking time 1～4 hour; Obtaining the surface has aluminium titanates coating refractory particle, and specific embodiments is seen table 3.Amorphous refractory size distribution such as Fig. 1 before being untreated, wherein 1 silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel, magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, slag, ferrochrome slag or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck aluminium titanates is arranged with this method gained surface; Wherein 2 is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel, magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, slag, ferrochrome slag or expanded vermiculite matrix, the 3rd, and the metatitanic acid aluminium lamination; With this method gained surface its part sectioned view of spherical fire resisting material particle such as Fig. 3 of one deck Calcium Fluoride (Fluorspan) are arranged, wherein 3 is metatitanic acid aluminium laminations, the 4th, and alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball or float the pearl matrix.
Table 3 metatitanic acid aluminium powder modified surface fire resisting material particle is handled under differing temps
Claims (8)
1. a fire resisting material particle is characterized in that: in the fire resisting material particle surface coverage one deck aluminium titanates is arranged; Massfraction is 0.05 ~ 50% aluminium titanates.
2. a kind of fire resisting material particle as claimed in claim 1 is characterized in that: described fire resisting material particle is compact refractory material particle or lightweight refractory particle, and fire resisting material particle is of a size of 1 micron～15 centimetres.
3. a kind of fire resisting material particle as claimed in claim 2; It is characterized in that: described compact refractory material particle is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, spinel; Magnesite clinker, electrosmelted magnesite clinker, forsterite, konite, serpentine, sillimanite, Irish touchstone, scum, ferrochrome slag or slag.
4. a kind of fire resisting material particle as claimed in claim 2 is characterized in that: described lightweight refractory particle is alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball, floats pearl or expanded vermiculite.
5. as claimed in claim a kind of preparation method of fire resisting material particle is characterized in that the step of this method is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2 ~ 0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8% Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 fire resisting material particle is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the fire resisting material particle surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the fire resisting material particle of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
6. the preparation method of a kind of fire resisting material particle as claimed in claim 5, it is characterized in that: fire resisting material particle is compact refractory material particle or lightweight refractory particle, fire resisting material particle is of a size of 1 micron～15 centimetres.
7. the preparation method of a kind of fire resisting material particle as claimed in claim 6, it is characterized in that: described compact refractory material particle is silica, fused quartz, alabaster, flint clay, calcined clay, alumine, alundum, fused corundom, magnesite clinker, electrosmelted magnesite clinker, forsterite, serpentine, scum or slag.
8. the preparation method of a kind of fire resisting material particle as claimed in claim 6, it is characterized in that: described lightweight refractory particle is alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball, floats pearl, haydite, perlite or expanded vermiculite.
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|---|---|---|---|
| CN2012100071328A CN102584269A (en) | 2012-01-11 | 2012-01-11 | Refractory material granules with aluminum titanate coatings and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014764A (en) * | 2014-05-22 | 2014-09-03 | 泰州市旺鑫耐火材料有限公司 | Ceramic sprue gate bushing for low pressure casting of aluminum alloy and manufacturing method thereof |
| CN111995417A (en) * | 2020-08-21 | 2020-11-27 | 浙江锦诚新材料股份有限公司 | Magnesium aluminate spinel castable for aluminum melting furnace |
| CN112759370A (en) * | 2019-10-18 | 2021-05-07 | 三达膜科技（厦门）有限公司 | Preparation method of high-strength ceramic filtering membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045828A (en) * | 2006-07-03 | 2007-10-03 | 张义纲 | Phosphate film-coated powder and preparation method thereof |
| CN101734935A (en) * | 2009-12-24 | 2010-06-16 | 中钢集团洛阳耐火材料研究院有限公司 | Aluminium liquid infiltration-resistant high-aluminum plastic material and preparation method |
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2012
- 2012-01-11 CN CN2012100071328A patent/CN102584269A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045828A (en) * | 2006-07-03 | 2007-10-03 | 张义纲 | Phosphate film-coated powder and preparation method thereof |
| CN101734935A (en) * | 2009-12-24 | 2010-06-16 | 中钢集团洛阳耐火材料研究院有限公司 | Aluminium liquid infiltration-resistant high-aluminum plastic material and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014764A (en) * | 2014-05-22 | 2014-09-03 | 泰州市旺鑫耐火材料有限公司 | Ceramic sprue gate bushing for low pressure casting of aluminum alloy and manufacturing method thereof |
| CN112759370A (en) * | 2019-10-18 | 2021-05-07 | 三达膜科技（厦门）有限公司 | Preparation method of high-strength ceramic filtering membrane |
| CN111995417A (en) * | 2020-08-21 | 2020-11-27 | 浙江锦诚新材料股份有限公司 | Magnesium aluminate spinel castable for aluminum melting furnace |
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