CN102295463A - Zirconia corundum hollow sphere and preparation method thereof - Google Patents
Zirconia corundum hollow sphere and preparation method thereof Download PDFInfo
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- CN102295463A CN102295463A CN2011101558632A CN201110155863A CN102295463A CN 102295463 A CN102295463 A CN 102295463A CN 2011101558632 A CN2011101558632 A CN 2011101558632A CN 201110155863 A CN201110155863 A CN 201110155863A CN 102295463 A CN102295463 A CN 102295463A
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Abstract
The invention relates to a zirconia corundum hollow sphere, containing 90-99.9% of Al2O3 and 0.1-10% of ZrO2 by mass. With various aluminium containing and zirconium containing substances as the main raw materials, the zirconia corundum hollow sphere is prepared by the steps of adding an additive to adjust melt components and viscosity, conducting smelting in a three-phase AC (alternating current) ore-smelting electric arc furnace or a direct current ore-smelting electric arc furnace, pouring out the melt which is then subjected to air injection, and carrying out screening, thus obtaining a zirconia corundum hollow sphere of 0.2-5mm. The invention provides a zirconia corundum hollow sphere simultaneous simultaneously with low cost, wear resistance, erosion resistance, thermal shock resistance as well as good applicability, and its preparation method.
Description
Technical field
The present invention relates to belong to technical field of refractory materials, especially a kind of hollow ball and preparation method thereof.
Background technology
In traditional energy exhaustion and today of new forms of energy slower development day by day, the most urgent current task is that exploitation lightweight, high-strength, good thermal shock stability, use temperature high energy satisfy the required inner lining material of light structures High Temperature Furnaces Heating Apparatus, change that traditional ultrahigh-temperature kiln is big owing to the thermal capacity that adopts the heavy structure to exist, temperature rise rate is low, energy consumption is big, work-ing life is short, maintenance capacity in mid-term shortcoming such as big, save energy, cut down the consumption of energy, for building a resource-conserving society and the human kind sustainable development service.
Because light heat insulation material is to obtain lower thermal conductivity by the mode of introducing pore, introduce serious, the compressive strength reduction of the raising of heavily burning linear shrinkage ratio, refractoriness under load reduction, high temperature creep that a large amount of pores can cause light material, thereby the use temperature that makes lagging material is difficult to improve, and range of application is restricted, therefore seeking new method prepares the focus that new high temperature insulating material is the various countries expert always.In existing lagging material, aluminum oxide lagging material kind is maximum, the use temperature height, heat-insulating and energy-saving is effective, it is the lagging material of giving priority to now, wherein the application of lightweight alumina hollow ball pottery is a sign of lagging material technical progress, it has overcome, and original foamed alumina product strength is low, the shortcoming of high-temperature creep resistance difference, can directly contact flame, also can be used as high temperature inner lining structure material uses, can promote the transformation of conventional high-temperature furnace construction, for design novel kiln structure lays the foundation.Alumina hollow ball is a kind of high temperature insulating material of excellent performance, it is to form with the higher aluminum oxide melting blowing in electric furnace of purity, with the alumina hollow ball is that main body can be made into the different shape goods, 1800 ℃ of maximum operation (service) temperatures, products machinery intensity height, be the several times of general light weight product, and volume density can reach corundum products half in addition lower.Employing can also be prepared the zirconium white hollow ball with quadrat method, and use temperature also can reach more than 2100 ℃, but because therefore the zirconium white expensive raw material price is difficult to large-scale promotion application in industrial production.Simultaneous oxidation aluminium hollow ball is difficult to obtain large-scale application also because of cost performance, and with respect to the total amount of refractory materials, ratio is less.The hollow ball of present existing several materials, the temperature that needs in the fusion process is higher, not only quite high with electric energy consumption, preparation condition is required very harsh, for relevant auxiliary facility acid test is arranged all, and composition is more single, and the performance at aspects such as anti-erosion, heat-shock resistances has much room for improvement, and use range also is restricted.Be further to expand the range of application of hollow ball, particularly successfully develop, establish the basis of electric smelting hollow ball step large-scale application based on the proposition and the portioned product of the structure/heat-insulating integrated composite brick notion of hollow ball.Both structure/heat-insulating integrated composite brick be composited by heavy working lining/light heat insulation layer, and the different components working lining needs the electric smelting hollow ball coupling of different components, otherwise is prone to surface reaction, influences product properties.
In addition, mould material based on low-cost electric smelting hollow ball occurs, different environment for use conditions has put forward different component requirements, the electric smelting hollow ball that requires that has has better heat-shock resistance, what have requires better wear resistance and corrosion resistance strong, the requirement low cost that has, these all need the raw material of different components and different costs specifically to satisfy these requirements.
Summary of the invention
Can not take into account low cost, wear resistance and corrosion resistance and heat-shock resistance, the relatively poor deficiency of suitability for what overcome existing hollow ball and preparation method thereof, the invention provides and to take into account low cost, wear resistance and corrosion resistance and heat-shock resistance simultaneously, have zircon corundum hollow ball of good applicability and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of zircon corundum hollow ball contains Al in the described zircon corundum hollow ball
2O
3And ZrO
2, wherein, Al
2O
3The quality percentage composition is 90～99.9%, ZrO
2The quality percentage composition is 0.1～10%.
Among the present invention, since purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
A kind of preparation method of zircon corundum hollow ball, described preparation method's step is as follows:
1) with aluminium-containing substance with contain zirconium material and mix in proportion, or with aluminium-containing substance, contain zirconium material and additive by the ratio requirement mixing, obtain admixtion;
2) admixtion is dropped in three-phase or the direct current electric arc furnace, adjust electric current and voltage, until fusion, refining 10～80 minutes makes Al in the melt 2200～2800 ℃ of meltings
2O
3+ ZrO
2The quality percentage composition is not less than 90%;
3) melting finishes, the turndown winding-up;
4) ball is sieved the zircon corundum hollow ball that obtains 0.2～5mm.
Further, described aluminium-containing substance is one or more a arbitrary combination of commercial alumina, aluminium hydroxide, alumine or aluminium slag.
The described zirconium material that contains is zircon or monoclinic zirconia.
Described additive is a carbon materials, and as the desiliconization material, consumption is SiO in the admixtion
21.2～4 times of mole number.
Described additive is the mixture of carbon materials and iron content component substances, and the carbon materials consumption is SiO in the admixtion
20.8～3 times of mole number, the iron molar content is SiO in the admixtion in the iron content component substances
22～5 times of mole number.
Described carbon materials is graphite, refinery coke, forge one or more the arbitrary combination in back Jiao, coal, coke, pitch or the charcoal.
Described iron content component substances is one or more the arbitrary combination in iron filings, iron ore, iron oxide red, iron oxide black, scrap iron or the steel scrap.
Among the present invention, the know-why of institute's foundation is for various aluminium-containing substances or to contain zirconium material be main raw material, introduce additive simultaneously and adjust melt composition and viscosity, make the zircon corundum hollow ball, make it to have the functional character different with the hollow ball of other components by the winding-up melt.
Beneficial effect of the present invention mainly shows: prepared zircon corundum hollow ball has characteristics such as compressive strength height, fracture toughness property be good, and thermal and insulating performance is good, be especially suitable for use as the aggregate in lagging material and the lightening casting material, the heat insulating requirement of low temperature working conditions in can satisfying.
Embodiment
Below the present invention is further described.
Embodiment 1:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.2%, ZrO
2The quality percentage composition be 4.8%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, and wherein commercial alumina 95% and monoclinic zirconia 5% adopt refinery coke, forge back Jiao and iron filings as additive, refinery coke and forge the burnt consumption in back and guarantee that the C molar weight is SiO in the batching
20.8 times of molar weight, the consumption of iron filings guarantee that the Fe molar weight is SiO in the batching
22 times of molar weight; The raw material back of working good was mixed in ball mill 1 hour; Admixtion is dropped in the three-phawse arc furnace, adjust electric current and voltage 2800 ℃ of meltings to fusion, refining 10 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.2%, ZrO
2The quality percentage composition be 4.8%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 2:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.4%, ZrO
2The quality percentage composition be 4.6%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, and wherein commercial alumina 93% and zircon 7% adopt graphite as additive, and the consumption of graphite guarantees that the C molar weight is SiO in the batching in the graphite
24 times of molar weight; The raw material back of working good was mixed in ball mill 1 hour; Admixtion is dropped in the three-phawse arc furnace, adjust electric current and voltage 2200 ℃ of meltings, refining 40 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.4%, ZrO
2The quality percentage composition be 4.6%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 3:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 92.5%, ZrO
2The quality percentage composition be 2.5%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, and wherein aluminium slag 94%, zircon 3% and monoclinic zirconia 1% adopt coke, charcoal and iron ore as additive, and the consumption of coke and charcoal guarantees that the C molar weight is SiO in the batching
23 times of molar weight, the consumption of iron ore guarantee that the Fe molar weight is SiO in the batching
22 times of molar weight; The raw material back of working good was mixed in ball mill 1.6 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2200 ℃ of meltings to fusion, refining 80 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 92.5%, ZrO
2The quality percentage composition be 2.5%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 4:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.9%, ZrO
2The quality percentage composition be 4.1%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, wherein commercial alumina 45%, alumine 50%, zircon 3% and monoclinic zirconia 2%, adopt graphite, refinery coke, scrap iron, iron and iron oxide red as additive, the consumption of graphite, refinery coke guarantees that the C molar weight is SiO in the batching
20.8 times of molar weight, the consumption of scrap iron, iron and iron oxide red guarantee that the molar weight of Fe is SiO in the batching
25 times of molar weight; The raw material back of working good was mixed in ball mill 1.8 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2300 ℃ of meltings to fusion, refining 20 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of chromium corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.9%, ZrO
2The quality percentage composition be 4.1%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 5:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.4%, ZrO
2The quality percentage composition be 4.6%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, and wherein aluminium hydroxide 96%, zircon 2.5%, high-purity monoclinic zirconia 1.5% adopt and forge back Jiao, iron oxide black and steel scrap as additive, forges the burnt consumption in back and guarantees that the C molar weight is SiO in preparing burden
22 times of molar weight, the consumption of iron oxide black and steel scrap guarantee that the Fe molar weight is SiO in the batching
23.5 times of molar weight; The raw material back of working good was mixed in ball mill 1.6 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2500 ℃ of meltings to fusion, refining 30 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.4%, ZrO
2The quality percentage composition be 4.6%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 6:
In the present embodiment, Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.9%, ZrO
2The quality percentage composition be 4.1%, the quality percentage composition of other materials is 5% because purification technique restriction in material purity and the production technique, Al
2O
3And ZrO
2Quality percentage composition sum contains a certain amount of other material less than 100% in the hollow ball, but does not influence use.
The preparation method is: proportioning raw materials adopts the quality percentage composition, and wherein alumine 94.5%, zircon 5.5% adopt pitch, coal and iron filings as additive, and the consumption of pitch and coal guarantees that the C molar weight is SiO in the batching
20.8 times of molar weight, the consumption of iron filings guarantee that the Fe molar weight is SiO in the batching
25 times of molar weight; The raw material back of working good was mixed in ball mill 1.9 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2800 ℃ of meltings to fusion, refining 10 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.9%, ZrO
2The quality percentage composition be 4.1%, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 7
Proportioning raw materials adopts quality percentage composition, wherein high purity aluminium hydroxide [Al (OH)
3The quality percentage composition greater than 99.99%] 99.93% and high-purity monoclinic zirconia [ZrO
2The quality percentage composition greater than 99.99%] 0.07%; The raw material back of working good was mixed in ball mill 1.9 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2800 ℃ of meltings to fusion, refining 10 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 99.9%, ZrO
2The quality percentage composition be 0.1%,, product can be used as high-strength light mould material and light cinder brick aggregate.
Embodiment 8
Proportioning raw materials adopts quality percentage composition, wherein high purity aluminium hydroxide [Al (OH)
3The quality percentage composition greater than 99.99%] 93.23% and high-purity monoclinic zirconia [ZrO
2The quality percentage composition greater than 99.99%] 6.77%; The raw material back of working good was mixed in ball mill 1.9 hours; Admixtion is dropped in the direct current electric arc furnace, adjust electric current and voltage 2800 ℃ of meltings to fusion, refining 10 minutes; Melting finishes, the turndown winding-up; The ball screening is obtained the high temperature resistant hollow ball of zircon corundum of 0.2～5mm.Al in the high temperature resistant hollow ball of zircon corundum
2O
3The quality percentage composition is 90.0%, ZrO
2The quality percentage composition be 10.0%,, product can be used as high-strength light mould material and light cinder brick aggregate.
The foregoing description only is for example clearly is described, is not the qualification that embodiment is done.For the person of an ordinary skill in the technical field; can also make other multi-form variation or changes on the basis of the above description; can't give an example one by one to all embodiments at this, and draw the conspicuous variation of extension thus or change still within the protection domain of the invention.
Claims (8)
1. a zircon corundum hollow ball is characterized in that: contain Al in the described zircon corundum hollow ball
2O
3And ZrO
2, wherein, Al
2O
3The quality percentage composition is 90～99.9%, ZrO
2The quality percentage composition is 0.1～10%.
2. the preparation method of a zircon corundum hollow ball as claimed in claim 1, it is characterized in that: described preparation method's step is as follows:
1) with aluminium-containing substance with contain zirconium material and mix in proportion, or with aluminium-containing substance, contain zirconium material and additive by the ratio requirement mixing, obtain admixtion;
2) admixtion is dropped in three-phase or the direct current electric arc furnace, adjust electric current and voltage, until fusion, refining 10～80 minutes makes Al in the melt 2200～2800 ℃ of meltings
2O
3+ ZrO
2The quality percentage composition is not less than 90%;
3) melting finishes, the turndown winding-up;
4) ball is sieved the zircon corundum hollow ball that obtains 0.2～5mm.
3. the preparation method of zircon corundum hollow ball as claimed in claim 2 is characterized in that: described aluminium-containing substance is one or more a arbitrary combination of commercial alumina, aluminium hydroxide, alumine or aluminium slag.
4. the preparation method of zircon corundum hollow ball as claimed in claim 2 is characterized in that: the described zirconium material that contains is zircon or monoclinic zirconia.
5. the preparation method of zircon corundum hollow ball as claimed in claim 2 is characterized in that: described additive is a carbon materials, and as the desiliconization material, consumption is SiO in the admixtion
21.2～4 times of mole number.
6. the preparation method of zircon corundum hollow ball as claimed in claim 2 is characterized in that: described additive is the mixture of carbon materials and iron content component substances, and the carbon materials consumption is SiO in the admixtion
20.8～3 times of mole number, the iron molar content is SiO in the admixtion in the iron content component substances
22～5 times of mole number.
7. as the preparation method of claim 5 or 6 described zircon corundum hollow balls, it is characterized in that: described carbon materials is graphite, refinery coke, forge one or more the arbitrary combination in back Jiao, coal, coke, pitch or the charcoal.
8. the preparation method of zircon corundum hollow ball as claimed in claim 6 is characterized in that: described iron content component substances is one or more the arbitrary combination in iron filings, iron ore, iron oxide red, iron oxide black, scrap iron or the steel scrap.
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|---|---|---|---|
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| CN201110145172.4 | 2011-05-31 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557698A (en) * | 2012-03-15 | 2012-07-11 | 浙江大学苏州工业技术研究院 | Aluminum-containing hollow sphere light-weight brick and preparation method thereof |
| CN102584303A (en) * | 2012-03-15 | 2012-07-18 | 浙江大学苏州工业技术研究院 | Alkaline bubble brick and preparation method thereof |
| CN102875173A (en) * | 2012-10-19 | 2013-01-16 | 郑州振中电熔锆业有限公司 | Method for purifying ground zircon corundum brick powder |
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| CN102875173B (en) * | 2012-10-19 | 2014-08-27 | 郑州振中电熔新材料有限公司 | Method for purifying ground zircon corundum brick powder |
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Application publication date: 20111228 |