CN102584265A - Refractory material granules with calcium fluoride layers on surfaces and preparation method for refractory material granules - Google Patents
Refractory material granules with calcium fluoride layers on surfaces and preparation method for refractory material granules Download PDFInfo
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- CN102584265A CN102584265A CN2012100070289A CN201210007028A CN102584265A CN 102584265 A CN102584265 A CN 102584265A CN 2012100070289 A CN2012100070289 A CN 2012100070289A CN 201210007028 A CN201210007028 A CN 201210007028A CN 102584265 A CN102584265 A CN 102584265A
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Abstract
The invention discloses refractory material granules with calcium fluoride layers on surfaces and a preparation method for the refractory material granules. The preparation method comprises the following steps of: preparing an aqueous solution of a fluorine-containing compound, an aqueous solution of a calcium-containing compound, calcium fluoride sol and calcium fluoride powder slurry; and performing surface coating and heat treatment on the surfaces of the refractory material granules, so that a layer of calcium fluoride covers the surfaces of the refractory material granules. The calcium fluoride has the characteristic of not infiltrating aluminum, so the treated refractory material granules do not infiltrate the aluminum. The calcium fluoride enters 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 relating to a kind of surface has fire resisting material particle of Calcium Fluoride (Fluorspan) layer and preparation method thereof.
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 Calcium Fluoride (Fluorspan) 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.
Summary of the invention
The object of the present invention is to provide a kind of surface that fire resisting material particle of Calcium Fluoride (Fluorspan) layer and preparation method thereof is arranged, utilize existing fire resisting material particle, make the fire resisting material particle surface have one deck cannot not possess stickingly the Calcium Fluoride (Fluorspan) of aluminium characteristic as starting material.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
One, there is the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface:
Be covered with one deck massfraction on the fire resisting material particle surface and be 0.05～50% Calcium Fluoride (Fluorspan).
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, 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, haydite, perlite or expanded vermiculite.
Two, there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface, and the step of this method is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 fire resisting material particle is immersed in the fluorochemicals aqueous solution oven dry; And then the refractory materials that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on fire resisting material particle; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the fire resisting material particle that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on fire resisting material particle;
2.4 fire resisting material particle is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of fire resisting material particle, oven dry gets final product;
(3) thermal treatment:
The fire resisting material particle that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
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 successively to soak or the spraying fluoride ion aqueous solution and the calcium ions aqueous solution or the method for directly spraying Calcium Fluoride (Fluorspan) powdery pulp, Calcium Fluoride (Fluorspan) colloidal sol are carried out surface-treated.Calcium Fluoride (Fluorspan) adheres to the surface of fire resisting material particle, and gets into the slit, and in crackle and the hole, dry back Calcium Fluoride (Fluorspan) is distributed in the fire resisting material particle surface, slit and intergranule.Calcium Fluoride (Fluorspan) and fire resisting material particle sintering under the condition of being heated.Because Calcium Fluoride (Fluorspan) has pair aluminium liquid that not imbibition characteristic is arranged, thereby treated fire resisting material particle has aluminium imbibition characteristic not.And Calcium Fluoride (Fluorspan) gets among fire resisting material particle crackle and the hole, ability mended crack and hole behind the high temperature sintering, thus improve fire resisting material particle intensity.
Description of drawings
Fig. 1 is fire resisting material particle graphicrepresentation in irregular shape.
Fig. 2 is a fire resisting material particle part sectioned view in irregular shape.
Fig. 3 is spherical fire resisting material particle part sectioned view.
Among the figure: 1, fire resisting material particle in irregular shape, 2, fire resisting material particle matrix in irregular shape, 3, the Calcium Fluoride (Fluorspan) layer, 4, spherical fire resisting material particle matrix.
Embodiment
Embodiment 1: (immersion)
Configure the fluoride ion aqueous solution and the calcium ions aqueous solution earlier, fire resisting material particle is immersed in the fluoride ion aqueous solution, will be immersed in the calcium ions aqueous solution through the fire resisting material particle that the fluoride ion aqueous solution was handled again after the oven dry; Make it the surface and generate Calcium Fluoride (Fluorspan); Behind the washing and drying, put into High Temperature Furnaces Heating Apparatus thermal treatment, thermal treatment temp is 800～1200 ℃; Soaking time is 1～4 hour, obtains the fire resisting material particle that there is one deck Calcium Fluoride (Fluorspan) on the surface at last.Specific embodiments is seen table 1.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, haydite, perlite or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck Calcium Fluoride (Fluorspan) 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, haydite, perlite or expanded vermiculite matrix, the 3rd, and the Calcium Fluoride (Fluorspan) layer; 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 Calcium Fluoride (Fluorspan) layers, the 4th, and alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball or float the pearl matrix.
Table 1 precipitator method Calcium Fluoride (Fluorspan) modification fire resisting material particle is handled under differing temps
Embodiment 2 (spraying)
Configure the fluoride ion aqueous solution and the calcium ions aqueous solution earlier, the fluoride ion aqueous solution is sprayed on the fire resisting material particle surface, oven dry; And then the calcium ions aqueous solution is sprayed on sprayed the fluoride ion aqueous solution fire resisting material particle surface to moistening, reaction generates the Calcium Fluoride (Fluorspan) deposition, the washing oven dry; Put into High Temperature Furnaces Heating Apparatus thermal treatment; Thermal treatment temp is 800～1200 ℃, and soaking time is 1～4 hour, and obtaining fire resisting material particle at last has one deck Calcium Fluoride (Fluorspan).Specific embodiments is 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, haydite, perlite or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck Calcium Fluoride (Fluorspan) 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, haydite, perlite or expanded vermiculite matrix, the 3rd, and the Calcium Fluoride (Fluorspan) layer; 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 Calcium Fluoride (Fluorspan) layers, 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 spraying method Calcium Fluoride (Fluorspan) modification fire resisting material particle is handled under differing temps
Embodiment 3: (spraying)
With commercial or self-control calcium fluoride powder system form slurry, the Calcium Fluoride (Fluorspan) massfraction is 10%, 15%, 18% in the slurry; 22%, 26%, 30% is sprayed on the fire resisting material particle surface to moistening fully; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 800 ℃～1200 ℃.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, haydite, perlite or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck Calcium Fluoride (Fluorspan) 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, haydite, perlite or expanded vermiculite matrix, the 3rd, and the Calcium Fluoride (Fluorspan) layer; 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 Calcium Fluoride (Fluorspan) layers, 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 spraying method Calcium Fluoride (Fluorspan) slurry modification fire resisting material particle is handled under differing temps
Embodiment 4: (spraying)
Commercial Calcium Fluoride (Fluorspan) colloidal sol is configured to the Calcium Fluoride (Fluorspan) colloidal sol of various solubility; The Calcium Fluoride (Fluorspan) massfraction is 5%, 15%, 25% in the colloidal sol; Be sprayed on fire resisting material particle surface to moistening fully or fire resisting material particle is immersed in the Calcium Fluoride (Fluorspan) colloidal sol; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 600 ℃～900 ℃.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, haydite, perlite or expanded vermiculite.Its part sectioned view of fire resisting material particle in irregular shape such as Fig. 2 that one deck Calcium Fluoride (Fluorspan) 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, haydite, perlite or expanded vermiculite matrix, the 3rd, and the Calcium Fluoride (Fluorspan) layer; 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 Calcium Fluoride (Fluorspan) layers, the 4th, and alumina hollow ball, corundum bollow ball, magnesium-aluminium spinel hollow ball, aluminium calcium hollow ball or float the pearl matrix.
Claims (9)
1. there is the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a surface, it is characterized in that: be covered with one deck massfraction on the fire resisting material particle surface and be 0.05 ~ 50% Calcium Fluoride (Fluorspan).
2. there is the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface as claimed in claim 1, it 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. there is the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface 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, serpentine, sillimanite, Irish touchstone scum, ferrochrome slag or slag.
4. there is the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface as claimed in claim 2, 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.
5. there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on as claimed in claim a kind of surface, it is characterized in that the step of this method is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 fire resisting material particle is immersed in the fluorochemicals aqueous solution oven dry; And then the refractory materials that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on fire resisting material particle; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the fire resisting material particle that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on fire resisting material particle;
2.4 fire resisting material particle is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of fire resisting material particle, oven dry gets final product;
(3) thermal treatment:
The fire resisting material particle that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
6. there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface according to claim 3, it is characterized in that:
The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
7. there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface as claimed in claim 5, it is characterized in that: 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.
8. there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface 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.
9. there is the preparation method of the fire resisting material particle of Calcium Fluoride (Fluorspan) layer on a kind of surface 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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| CN2012100070289A CN102584265A (en) | 2012-01-11 | 2012-01-11 | Refractory material granules with calcium fluoride layers on surfaces and preparation method for refractory material granules |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103011852A (en) * | 2012-11-26 | 2013-04-03 | 中国铝业股份有限公司 | Non-sintering densification method of corundum castable product |
| CN104119587A (en) * | 2014-07-02 | 2014-10-29 | 合肥和安机械制造有限公司 | Modified bauxite for high-temperature-resistant high-pressure-resistant rubber tube material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011852A (en) * | 2012-11-26 | 2013-04-03 | 中国铝业股份有限公司 | Non-sintering densification method of corundum castable product |
| CN103011852B (en) * | 2012-11-26 | 2015-02-04 | 中国铝业股份有限公司 | Non-sintering densification method of corundum castable product |
| CN104119587A (en) * | 2014-07-02 | 2014-10-29 | 合肥和安机械制造有限公司 | Modified bauxite for high-temperature-resistant high-pressure-resistant rubber tube material and preparation method thereof |
| CN104119587B (en) * | 2014-07-02 | 2016-03-30 | 合肥和安机械制造有限公司 | A kind of high temperature high voltage resistant hose material modified aluminium alumina and preparation method thereof |
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Application publication date: 20120718 |